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2018 Radical Reactions to Form Expanded Polyaromatics: Electronic and Steric Control Audrey Marie Hughes

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COLLEGE OF ARTS AND SCIENCES

RADICAL REACTIONS TO FORM EXPANDED POLYAROMATICS:

ELECTRONIC AND STERIC CONTROL

AUDREY MARIE HUGHES

A Dissertation submitted to the Department of Chemistry and Biochemistry in partial fulfillment of the requirements for the degree of Doctor of Philosophy

2018 Audrey Marie Hughes defended this dissertation on November 7, 2018. The members of the supervisory committee were:

Igor V. Alabugin Professor Directing Dissertation

Bruce R. Locke University Representative

Kenneth Hanson Committee Member

Wei Yang Committee Member

The Graduate School has verified and approved the above-named committee members and certifies that the dissertation has been approved in accordance with university requirements.

ii TABLE OF CONTENTS

List of Tables ...... v List of Figures ...... vi List of Schemes ...... viii Abstract ...... xi

1. EXO-DIG RADICAL CASCADES OF SKIPPED ENEDIYNES: BUILDING A NAPHTHALENE MOIETY WITHIN A POLYCYCLIC FRAMEWORK ...... 1

1.1 Introduction ...... 1 1.2 Results and Discussion ...... 2 1.2.1 Substrate Design ...... 2 1.2.2 Cascade Transformation...... 3 1.3 Conclusion ...... 7

2. TRACELESS DIRECTING GROUPS IN RADICAL CASCADES: FROM OLIGOALKYNES TO FUSED HELICENES WITHOUT TETHERED INITIATORS ...... 8

2.1 Introduction ...... 8 2.2 Results and Discussion ...... 11 2.2.1 Chemoselectivity in Radical Cascades ...... 14 2.2.2 Barriers for the Cyclization of Vinyl Radicals ...... 17 2.2.3 Full Radical Cascade and Return of the Radical at the β-Carbon ...... 18 2.2.4 Functionalization of Stannyl Benzofluorenes ...... 20 2.2.5 Formation of Larger Polyaromatic Systems ...... 21 2.2.6 Selected Photophysical Properties of Benzo[a]fluorene Chromophores ...... 22 2.3 Conclusion ...... 23

3. RADICAL ALKYNE PERI-ANNULATION REACTIONS FOR THE SYNTHESIS OF FUNCTIONALIZED PHENALENES, BENZANTHRENES, AND OLYMPICENE ...... 24

3.1 Introduction ...... 24 3.2 Results and Discussion ...... 27 3.2.1 Computational Analysis ...... 29 3.3 Conclusion ...... 33

4. ELECTRONIC AND STERIC CONTROL OF RADICAL PERI-CYCLIZATIONS ON ROUTE TO EXPANDED POLYAROMATICS ...... 34

4.1 Introduction ...... 34 4.2 Results and Discussion ...... 36 4.2.1 Substituent Effects: Direct Substitution at the Alkyne ...... 37

iii 4.2.2 Indirect Substituent Effects: Presence and Orientation of a Methoxy Group at the Propargylic Carbon ...... 38 4.2.3 Effect of the Aromatic Target ...... 40 4.2.4 The Role of Aromaticity ...... 44 4.2.5 Stereoelectronic Effects in Peri-cyclizations ...... 46 4.2.6 Analysis of the 5-membered Cycle Formation ...... 48 4.2.7 Comparison of Alkyne and Peri-cyclizations ...... 49 4.3 Conclusion ...... 50

APPENDICES ...... 52

A. CHAPTER ONE SUPPORTING INFORMATION ...... 52 B. CHAPTER TWO SUPPORTING INFORMATION ...... 73 C. CHAPTER THREE SUPPORTING INFORMATION ...... 102 D. CHAPTER FOUR SUPPORTING INFORMATION ...... 141

References ...... 179

Biographical Sketch ...... 189

iv LIST OF TABLES

Table 1. Scope of substrates for radical cascades...... 4

Table 2. 1-(2-Alkynylphenyl)propargyl methyl ethers...... 12

Table 3. Radical cascade of propargyl methyl ethers...... 13

Table 5. Crystal data and structure refinement for 3b...... 68

Table 6. Atomic coordinates and equivalent isotropic displacement parameters (Å2) for 3b. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor...... 69

Table 7. Screening against different reagents, initiators, and solvents...... 70

Table 8. Full scope of substrates for radical cascades...... 71

Table 9. Full scope of 1-(2-alkynylphenyl)propargyl methyl ethers...... 94

Table 10. Optimization of reaction conditions...... 95

Table 11. Further optimization of SnBu3 addition to alkyne 1a...... 95

Table 12. Full scope of radical cascade of propargyl methyl ethers...... 96

Table 13. Photophysical properties of select complexes in CH2Cl2...... 100

Table 14. Optimization of the Sn‐promoted radical cyclization of alkyne 6a.a ...... 140

v LIST OF FIGURES

Figure 1. Skipped diynes are readily available...... 2

Figure 2. Regioselectivity of radical attack agrees with the radical addition to the terminal aromatic system in the final cyclization step...... 6

Figure 3. Geometries and energies of the four diastereomeric fused helicenes 20b (only one of the two enantiomers is shown for each structure, ΔG and energies in kcal/mol at 110°C)...... 22

Figure 4. a. Possible patterns and strategies for cycloaddition annulations at an aromatic system; b. cyclization annulations; c. evolution of polyaromatic ribbon synthesis; d. benzannulative approaches to growth of carbon nanostructures...... 25

Figure 5. Graphene edge types and sites of reactivity with a peri-radical annulation at the zigzag edge...... 34

Figure 6. Top: the problem of two pentagonal “defects” in the preparation of polyaromatic ribbons from conjugated oligoalkynes. Bottom: Two structural design elements that help to avoid formation of five-membered rings: initiation from a skipped alkyne equipped with a traceless directing group and termination via a “peri-” cyclization. (TDG = Traceless Directing Group)...... 35

Figure 7. An example of peri-cyclization on an anthracene core and the products of oxidative and reductive workups...... 36

Figure 8. The scope of computational analysis of peri-cyclizations...... 36

Figure 9. Correlation of activation (∆G‡) and reaction (∆G) free energies for the two types of cyclizations of polyaromatic systems (energies in kcal/mol at 110°C)...... 38

Figure 10. Transition states of α-Ph-β-SnMe3-disubstituted biphenyl 46b and naphthalene 43b, illustrating the key orbitals interacting with the radical center...... 38

Figure 11. Steric effect on the cis-radical attack in the two...... 44

Figure 12. a. NICS(1) of vinyl radical species, bolded values represent the face attacked to form 6-membered cis-products (values are shielding in ppm), and b. aromaticity vs. reaction barrier for corresponding starting materials above...... 45

Figure 13. X-ray crystal data of compound 3b...... 67

Figure 14. The ORTEP for 54b and 3b. Probability level 50%. Crystallography provided by Hoa Phan...... 72

Figure 15. ORTEP diagram for 2a...... 97

Figure 16. ORTEP diagram for 2p-Sn...... 97

vi Figure 17. Calculated geometries of the four vinyl radicals A-D at the UM06-2X/LanL2DZ level of theory...... 98

Figure 18. Geometries of radical A and its TS for the 6-exo-dig cyclization...... 99

Figure 19. Geometries of radical D and its TS for the 5-exo-dig cyclization...... 99

Figure 20. Geometries of radical B and its TS for the 5-exo-dig cyclization...... 99

Figure 21. Normalized (a) absorption and (b) emission spectra of 2a, 2c, 2o, and 2q in CH2Cl2 at room temperature. The absorption spectra have been normalized with respect to absorption at 316 nm...... 100

Figure 22. Normalized (a) absorption and (b) emission spectra of 2a, 2u, and 8 in CH2Cl2 at room temperature. The absorption spectra have been normalized with respect to absorption at 316 nm...... 101

vii LIST OF SCHEMES

Scheme 1. Variations on radical cascade cyclizations of oligoalkynes for conjugated (left) and “skipped” substrates (right)...... 1

Scheme 2. Synthesis of 1,(2-alkynylphenyl)propargyl iodoethyl ethers. Reaction yields are given for R1 = R2 = Ph...... 3

Scheme 3. The two mechanistic alternatives for the proposed cascade...... 5

Scheme 4. Connection between benzannelated oligoalkynes and graphene ribbons...... 8

Scheme 5. Evolution of molecular design for the conversion of oligoalkynes into polyaromatic ribbons...... 9

Scheme 6. Translocation of radical coupled with loss of X...... 11

Scheme 7. Control experiments: effect of propargylic substitution on selectivity. (data obtained by a coauthor)...... 14

Scheme 8. Illustration[67] of the proposed radical pool concept for the cyclization of conjugated enynes (energies in kcal/mol)...... 15

Scheme 9. Intermolecular competition in radical hydrostannation of alkynes: propargylic ether 14a vs diphenyl acetylene (tolane) 15 (data obtained by coauthor)...... 16

Scheme 10. Relative free energies of the four vinyl radicals formed by radical attack at the triple bonds of the skipped enediyne 6a at 110°C (energies in kcal/mol, data obtained by coauthor). ..16

Scheme 11. Comparison of relative energies of the four vinyl radicals and barriers for their exo- dig cyclizations (energies in kcal/mol, data obtained by coauthor)...... 17

Scheme 12. Proposed mechanism of cascade cyclization...... 18

Scheme 13. Calculated energy profile for the cascade radical transformation of diyne 6a (ΔG and ΔG‡ energies in kcal/mol at 110°C)...... 19

Scheme 14. Derivatization of benzofluorenes using Stille and Suzuki coupling reactions (data obtained by coauthor)...... 20

Scheme 15. Oxidative dimerization of 17b (data obtained by coauthor)...... 20

Scheme 16. Cascade transformation of skipped tris-alkyne 19a (data obtained by coauthor)...... 21

Scheme 17. Cascade transformation of skipped tetraynes 20a, 21a, and 22a leads to the formation of diastereomeric helicenes (data obtained by coauthor)...... 21

viii Scheme 18. Computed kinetics and thermodynamics for intramolecular attack of a vinyl radical at the naphthyl and biphenyl core at the UM06-2X/6-31+G(d,p) level of theory (energies in kcal/mol)...... 26

Scheme 19. Peri-cyclization of 9-anthracenyl propargylic ether in reductive and oxidative regimes (data obtained by coauthors)...... 27

Scheme 20. Precursors (left), cyclization substrates (center) and products of radical peri- cyclizations (right) (data obtained by coauthors)...... 28

Scheme 21. Protodestannylation (left) and iodination (right) of product 27a-Sn. Cross-coupling approach to extended PAHs (bottom) (data obtained by coauthors)...... 29

Scheme 22. Computed cyclization barriers and reaction energies at the (U)M06-2X/LanL2DZ level at 110°C in kcal/mol. X = SnMe3...... 30

Scheme 23. Selected computational results for the proposed evolution of the initially formed cyclic species. Favorable intermediates and observed products are boxed. ΔG values at (U)M06- 2X/LanL2DZ at 110°C, in kcal/mol. Energies of intermediates D, E, F and additional energy comparisons are given in Appendix C...... 31

Scheme 24. Relative stabilities of benzanthrene derivatives where X = SnMe3, at (U)M06- 2X/LanL2DZ level at 110°C, in kcal/mol. Experimentally observed products are boxed...... 32

Scheme 25. Comparison of substituent effects in the vinyl radical cyclization at peri-position of a. naphthalene and b. ortho′-positions of biphenyl (energies in kcal/mol at 110°C)...... 37

Scheme 26. The large effect of propargylic substituent at the activation barrier for the peri- cyclization at naphthalene. The transition state energies are given relative to the most stable conformer of the reactant in the spirit of the Curtin-Hammett principle (energies in kcal/mol at 110°C)...... 39

Scheme 27. The vinyl radical cyclization in 1-substituted anthracene 30a and 9-substituted anthracene 23a (energies in kcal/mol at 110°C)...... 40

Scheme 28. The vinyl radical cyclization in 1-phenanthrene 34a and 9-phenanthrene 32a structures (energies in kcal/mol at 110°C)...... 41

Scheme 29. The vinyl radical cyclization in 1-pyrene 36a and 4-pyrene 47a structures (energies in kcal/mol at 110°C)...... 42

Scheme 30. Calculated reaction free energies and barriers for radical peri-cyclizations that form the trans-products (energies in kcal/mol at 110°C)...... 43

Scheme 31. The role of propargylic substituents in reactivity: comparison of C-O and C-F bonds (energies in kcal/mol at 110°C)...... 47

ix Scheme 32. a. Barriers and reaction energies for 5-membered ring formation in the naphthalene and phenathrene systems. b. Comparison of geometries for the cis- and trans-isomer formation in the naphthalene and phenathrene system (energies in kcal/mol at 110°C)...... 49

Scheme 33. Cascade product variation via alteration of vinyl radical target (energies in kcal/mol at 110°C)...... 50

Scheme 34. General synthetic scheme for the preparation of 1-(1-(2-iodoethoxy)-3-phenylprop- 2-yn-1-yl)-2-(phenylethynyl)benzene...... 52

Scheme 35. Typical procedure for the synthesis of 8-phenyl-2,8-dihydro-1h- benzo[1,2]fluorine[3,4- b]furan...... 53

Scheme 36. Synthetic scheme (A1) for the preparation of 1-(1-methoxy-3-phenylprop-2-yn-1- yl)-2-(phenylethynyl)benzene (6a)...... 73

Scheme 37. Synthetic scheme (A4) for the preparation of oligoalkynes to vary position B- compounds (1o) and (1e)...... 74

Scheme 38. Synthetic scheme (A5) for the preparation of oligoalkynes to vary position C- compound (1h)...... 75

Scheme 39. General procedure for the synthesis of 11-phenyl-11h-benzo[a]fluorene (2a)...... 76

Scheme 40. Selected electronic interactions (NBO analysis in kcal/mol) contributing to the structure and stability of the transition state of the radical additions to the bis-alkyne 1a to form the most stable radical A.a ...... 97

Scheme 41. Selected electronic interactions (NBO energies in kcal/mol) contributing to the structure and stability of three vinyl radicals A, C, and D.a ...... 98

Scheme 42. Additional pyrene isomer vinyl radical attack...... 128

Scheme 43. Hydrogen abstraction where X = SnMe3...... 130

Scheme 44. Hydrogen abstraction where X = H...... 130

Scheme 45. Relative stabilities of intermediates...... 131

x ABSTRACT

Radical cascade transformations of alkyne precursors open efficient, convenient, and atom- economical access to functionalized polyaromatic compounds. These reactions provide a selective sequence of cyclizations followed by controlled termination, offering products of increased structural complexity. First, selectivity of initiation can be guided either by steric and geometric constraints, a tethered initiator, or through a directing group placed near the desired point of attack, such as an alkoxy group. These methods ensure attack at the correct carbon of the central alkyne, the necessary point of initiation to result in a fully cyclized alkyne substrate. Second, decrease of geometric “defects” has been achieved by introducing a skipped carbon in the oligoalkyne starting material. Also, by designing a directing group that also fragments upon the completion of the cascade, the alkyl loop left over from tethered initiation can be eliminated. Terminating cyclizations are further optimized by the use of peri- attack at the zigzag edge of a strategically placed polyaromatic unit. A hexagon will be formed as a result of the peri-attack rather than a previously present pentagon from attack at a pendant phenyl group. Peri-cyclization is effected by the presence and spatial orientation of a “bystander” propargylic -OMe substituent. The two orientations of this substituent produce cis- or trans- isomers where the formation of the cis-products always proceed through a lower barrier than formation of the trans-products. In these lower energy transition states, the σC-OMe bond and the radical orbital are aligned with the C-Sn orbital whereas in the higher energy transition states the

σC-OMe bond is nearly orthogonal to the radical and the vinyl C-Sn bond. Furthermore, replacing the -OMe group with -F, even larger effects are seen on the cyclization barriers—this effect shows that varying the strength of the acceptor can be a useful tool in tuning rate and selectivity of radical reactions.

xi CHAPTER ONE

EXO-DIG RADICAL CASCADES OF SKIPPED ENEDIYNES: BUILDING A NAPHTHALENE MOIETY WITHIN A POLYCYCLIC FRAMEWORK

Chem. Eur. J. 2014, 20, 390–393

1.1 Introduction

Radical cascades are valuable methods of building large and varied polycyclic frameworks.[1–8] Radical reagents have an advantage over similar ionic reactions due to their relatively broad functional group tolerance, mild reaction conditions, and the combination of high reactivity with controllable selectivity.[9–13] When optimum conditions are achieved, these reactions are efficient synthetic strategies.[14–19] The high carbon content,[20–24] possibility of modular assembly via reliable cross-coupling chemistry, and controllable reactivity make alkynes attractive precursors for the quick construction of carbon-rich polycyclic frameworks and materials. Recently these features were utilized for the preparation of polyaromatic ribbons from oligoalkynes through selective radical[25,26] and metal-catalyzed cascade cyclizations,[27] each of which correspond to controlled “polymerization” of alkynes sandwiched between the two rows of aromatic rings (Scheme 1).

Scheme 1. Variations on radical cascade cyclizations of oligoalkynes for conjugated (left) and “skipped” substrates (right).

Such radical type approaches to making graphene-like nanoribbons succeed only if there is a selective initial attack at the central alkyne of the oligoalkyne precursor. Initial central alkyne attack is essential to fully converting alkyne moieties in the precursor to expanded polyaromatic

1 frameworks. This proceeds via a sequence of exo-dig cyclizations. For oligoalkynes with three triple bonds, such selectivity is achievable by the use of selective intermolecular SnBu3 radical attack at the central alkyne.[25] For systems with four alkyne moieties, selectivity was achieved through covalent attachment of the initiating group near the central alkyne—an intramolecular approach. This modification ensures that the first attack at the triple bond is restricted to attack at the central alkyne.[26] Because both approaches start with conjugated oligoalkynes, the first cyclization that involves two alkynes is the 5-exo cyclization. As a consequence, the “polyacetylene ribbon” formed from the oligoalkyne always starts with a pentagon. If additional modifications are made to the precursor, the presence of this pentagon can be avoided, and the first reaction between two alkynes can be a 6-exo-dig closure. A potential limitation of this approach is that the rate of 6-exo-dig cyclization is expected to be approximately 50-fold slower than the 5- exo-dig process.[28,29] The overall transformation presented in this chapter is an approach for building naphthalene moieties within polycyclic frameworks using a modified version of the previously utilized oligoalkyne precursors. This cascade reaction involves a key step—a highly efficient 6- exo cyclization—that paves the way for the preparation of graphene nanoribbons.

1.2 Results and Discussion

1.2.1 Substrate Design

Figure 1. Skipped diynes are readily available.

The alternative design incorporates a “skipped” carbon into the oligoalkyne reactant adjacent to the central alkyne. Earlier findings indicated that C-I bonds can be selectively activated in the presence of several alkyne moieties by the HSnBu3/AIBN system. As a result, the regioselective formation of the vinyl radical was achieved using a similar tethered initiator located at the “skipped” carbon. Starting materials 1a-5a are readily prepared from the respective 2-

2 bromobenzaldehydes by via the combination of Sonogashira cross-coupling and nucleophilic addition of acetylide anions to the aldehyde[30] (Figure 1). Sonogashira cross-coupling of 2-bromobenzaldehydes with alkynes proceeded to produce a collection of 2-(phenylethynyl)benzaldehydes in 70–84 % yields (Scheme 2). Subsequent treatment with arylethynyl lithium produced the “skipped” acetylenic alcohols or propargyl alcohols. The hydroxyl group in these compounds serves as a convenient point for the attachment of the pendant radical initiator. Treatment with ethyl bromoacetate produced the propargyl esters[31] in 60–70% overall yields. Reduction of the esters produced alcohols which were then converted by the Appel reaction into the requisite iodo precursors for the radical cascade.

Scheme 2. Synthesis of 1,(2-alkynylphenyl)propargyl iodoethyl ethers. Reaction yields are given for R1 = R2 = Ph.

1. 2. 2. Cascade Transformation Screening of reagents and initiators for the key transformation of 1,(2- alkynylphenyl)propargyl iodoethyl ether (1a) into dihydro-1H-benzo[1,2]fluoreno[3,4-b]furan

(1b) revealed that HSnBu3/AIBN (1.5 equiv/0.3 equiv) in toluene (110°C, 14 h) was the optimal choice, providing 1b in 80 % yield. This method of forming fused naphthalenes was evaluated for generality by reacting additional diynes 2b-5b under the optimized conditions (Table 1). The cascade was fully compatible with a variety of functionalization at the three rings present in the precursor—both acceptors and donors were tolerated. These results highlight the broad scope and selectivity of this method (see Appendix A for full scope). 3 Table 1. Scope of substrates for radical cascades.

The structures of the cascade products were confirmed in the case of compound 1b and 2b with X-ray crystallography. The flat conjugated core of the molecules (dihedral angles between the naphthyl and fused aryl systems in 1b and 2b are < 68°) facilitates conjugation between the alkoxy substituted naphthalene and the annealed aromatic rings. Significant changes observed in the UV spectra as a function of substitution suggest that electronic communication between the fused rings is efficient (see Appendix A for details). 4 Two possible mechanisms for this cascade reaction are shown in Scheme 3. The mechanism beings with a chemoselective formation of an alkyl radical A. Intermolecular attack of the SnBu3 radical at the C-I bond of reactant 1a results in a “tethered initiator.” It is worth note that the SnBu3 radical is chemoselective since it is well-known to attack similarly substituted alkynes.[32,33] A 5-exo-dig cyclization of intermediate A leads to the formation of the first cycle, vinyl radical intermediate B. The intermediate B undergoes 6-exo-dig cyclization at the remaining triple bond with the formation of a second vinyl radical C. The two possible mechanisms diverge at this point.

Scheme 3. The two mechanistic alternatives for the proposed cascade.

In the first path, the vinyl radical C abstracts a hydrogen from the adjacent phenyl group, producing aryl radical F. In the second path, the vinyl radical attacks the π-system of the phenyl

5 group, producing intermediate D. Although the Csp2-H bonds are relatively strong, the first path would avoid transient loss of aromaticity. The “translocated” aryl radical F produced via such H- abstraction can “return” to the initial site of attack via a 5-endo-trig cyclization.[34–38] Alternatively, the second path produces delocalized radical D capable of rearomatization via a fast 1,5-hydrogen shift. Such shifts were shown in previous work to have low activation barriers.[39] At this point, the two mechanisms converge to give the penultimate intermediate G. A final H-abstraction step provides the final dihydro-1H-benzo[1,2]fluoreno[3,4-b]furan product (1b).[40– 43] The difference between the two mechanisms is important in those nonsymmetrically substituted alkynes when the final ring formation can provide a mixture of products. In substrate 54b, the single observed isomer product corresponds to the more favorable direction of attack a the naphthalane moiety (confirmed by X-ray diffraction, see Appendix A for additional information).[41–43] This preference allows for differentiation between the two pathways (Figure 2). Absence of the alternate isomer product formation through β-attack clearly shows that the product is formed via a path that involves the intermediate D.

Figure 2. Regioselectivity of radical attack agrees with the radical addition to the terminal aromatic system in the final cyclization step.

6 1.3 Conclusion

Formation of substituted benzo[1,2]fluoreno[3,4-b]furan derivatives is achievable via intramolecular radical cascade cyclization. Cyclization of skipped enediynes through a sequence of 5-exo-dig and 6-exo-dig closures then attack at a terminal aromatic ring results in the formation of three new cycles. Subsequent aromatization furnishes the fused naphthalene products in high yields. This radical cascade provides an opportunity for the expansion of methods for the preparation of longer and wider polycyclic frameworks.

7 CHAPTER TWO

TRACELESS DIRECTING GROUPS IN RADICAL CASCADES: FROM OLIGOALKYNES TO FUSED HELICENES WITHOUT TETHERED INITIATORS

J. Am. Chem. Soc. 2015, 137, 1165−1180

2.1 Introduction

Directing and protecting groups are both useful and inconvenient.[44] Key chemical transformations in the presence of sensitive moieties often require such groups to achieve the desired chemo- and regioselectivity. However, when such reactions are completed, and the protecting or directing group is no longer needed, additional steps are required to convert them into the desired functional group. Unfortunately, the use of directing or protecting groups is often unavoidable for achieving adequate selectivity in cascade transformations of reactants with diverse functionalization.

Scheme 4. Connection between benzannelated oligoalkynes and graphene ribbons.

The problem of selectivity is highlighted in cascades aimed at the preparation of polyaromatic ribbons from conjugated[25,26] and skipped[45] oligoalkynes. The positioning of

8 alkynes between two rows of aromatic rings allows for controlled “polymerization” in a sequence of selective “all-exo” cyclizations.[27] Although the regioselectivity of cyclizations is well controlled by the exo preference for alkyne cyclizations,[9,11–13] the key remaining challenge in the design of these cascades involves achieving control over chemoselectivity of initial radical attack. Avoiding the creation of pentagonal units at the beginning and end points of the oligoalkyne cascade is a secondary challenge.

Scheme 5. Evolution of molecular design for the conversion of oligoalkynes into polyaromatic ribbons.

In order for all triple bonds in the oligoalkyne precursor to be consumed, the initial radical attack must occur exclusively at the central alkyne (Scheme 4).[9] The steric and electronic properties of the multiple alkyne units in the oligoalkyne are similar and, as a consequence, make 9 chemoselectivity difficult to achieve. Covalent attachment of a tethered initiator (“a weak link”) near the desired site of initial radical attack addressed the issue of chemoselectivity.[10] Proximity and geometric constraints directed the intramolecular trajectory to the correct alkyne. However, this solution was not ideal because the atoms of the tether remain in the final product. Furthermore, when conjugated oligoalkynes are used as reactants, ring formation from the first two alkyne moieties of benzannulated oligoalkynes proceed via a 5-exo-dig path (Scheme 5). As a result, the “polyacetylene ribbon” formed from the oligoalkyne always contains a pentagonal unit. Avoiding the presence of this pentagon can be achieved by ensuring that the first reaction between two alkynes is a 6-exo type reaction. Creating a “skipped” oligoalkyne—a starting material that contains one extra carbon in the chain of alternating benzene rings and alkynes— allows for the polyacetylene ribbon to start with a 6-membered ring. This chapter addresses a strategy for chemoselective reactions of oligoalkynes that does not rely on a tethered radical initiator. This strategy achieves selective intermolecular attack by using a directing group at the skipped alkyne to guide a tin radical to the correct position for cascade initiation. The directing group, a methoxy moiety, creates the optimal conditions for a full cascade. The use of O-directing functionalities in Sn-radical attack at alkynes has been documented[46–55] with many interesting examples in the recent work of Hale[56–59] and Organ.[60– 65] In order to avoid incorporation of the directing group in the final product, the sequence of bond forming and bond breaking steps in the cascade has to be coordinated to eliminate the directing group at the last step of the cascade, with concomitant aromatization of the polycyclic ribbon. Removal of the -OMe group is possible via translocation of the radical center from the “bottom” of the cascade back to the β-carbon relative to the departing group. As the radical positions itself at the initial site of attack, fragmentation of the -OMe group allows for a tethered initiator and directing group free polycyclic ribbon product (Scheme 6). Under this condition, the loss of directing group occurs via fast β-scission as the last part of a one-pot transformation, and thus, such group can be considered a traceless directing group.[66] not only does this new strategy provide a concise synthetic approach to the defect-free preparation of the top part of the polyaromatic ribbon but also retains the -SnBu3 substituent as a convenient synthetic handle for further synthetic modifications of the polycyclic framework.

Scheme 6. Translocation of radical coupled with loss of X.

2.2 Results and Discussion

The starting 1,(2-alkynylphenyl)propargyl methyl ethers are readily prepared from commercially available 2-bromobenzaldehydes via a combination of Sonogashira cross-coupling and nucleophilic addition of acetylide anions to the aldehyde. The lithiated alkoxide formed at the latter step can be converted either into a propargylic alcohol via protonation or into propargyl methyl ethers via in situ addition of iodomethane. The propargyl methyl ethers 6a-11a were synthesized with a variety of substituents and in good yields (55–90%) (Table 2). Screening of various radical reagents and initiators was carried out for the model transformation of 6a to 6b. A combination of HSnBu3 and AIBN in refluxing toluene was the most efficient. The reaction conditions were further optimized by changing molar ratio of HSnBu3 and AIBN and varying the flow rate using a syringe pump (see Appendix B for details). Maintaining a steady concentration of AIBN was found to be superior to adding it all at once at the beginning of the reaction. The addition of a 0.04 M HSnBu3/0.01 M AIBN mixture at the flow rate of 1 mL/h to a 0.03 M solution of substrate in toluene (110°C, 14 h) provided 6b in excellent (86%) yield.

Use of lower amounts of HSnBu3/AIBN led to incomplete conversions.

11 Table 2. 1-(2-Alkynylphenyl)propargyl methyl ethers.

The scope of this reaction is demonstrated by the successful cascade cyclizations of a selection of propargyl methyl ethers (Table 3). A range of substituents tolerated the reaction conditions, including both donor and acceptor groups introduced to the core and pendant benzene rings. As the result, selective introduction of substituents of varying electronic nature at specific positions on rings (Table 3) of the polycyclic product is possible. Although reaction conditions were not optimized for each of the substrates 7b-11b, the isolated yields remained consistently high for both the donor and the acceptor substituents (70–88%), indicating generality and robustness of this cascade transformation (see Appendix B for full scope).

12 Table 3. Radical cascade of propargyl methyl ethers.

A variation of the model transformation was also carried out to examine the role of the methoxy substituent in the radical cascade (Scheme 7). A free propargyl alcohol 12a and a “deoxygenated” analogue with a methylene bridge 13a were exposed to the optimized reaction conditions used for the methoxy containing substrate 6a. This study revealed that the oxygen does aid in the selectivity of radical attack. The hydroxyl group example 12a had comparable, but lower product yield, though with a longer reaction time. The reaction of deoxygenated substrate 13a was much less selective. Yields and reaction times for these experiments suggest that the presence of the oxygen substituent plays an important role in the selectivity of this cascade reaction.

Scheme 7. Control experiments: effect of propargylic substitution on selectivity. (data obtained by a coauthor).

The naphthalene and phenylene moieties in the benzofluorene skeleton of 11-phenyl-11H- benzo[a]fluorene 6b are approximately coplanar suggesting that efficient conjugation and electronic communication should be possible between the different parts of the molecule. On the other hand, the exocyclic aryl group is projected away from the polycyclic plane and oriented in a way that minimizes steric repulsion with the aromatic hydrogens. Chemo- and regioselectivity of Sn addition was confirmed by X-ray analysis in addition to 1H and 13C NMR (see Appendix B).

2.2.1 Chemoselectivity in Radical Cascades Chemoselectivity is a key challenge in the design of cascade transformations of multifunctional substrates. In a system, where functional groups are similar or almost identical (i.e., oligoalkynes), such challenge is especially formidable. It has been shown previously that an application of dynamic covalent chemistry toward reversible radical reactions of Sn-radicals and π-systems can be used for the design of sufficiently selective transformation.[67–69] For example, in reactions of aromatic enynes (Scheme 8), intermolecular radical attack can lead to the formation of four different radicals (each capable of two different cyclizations). The formation of a single product was observed from a possibility of eight different cyclic structures. The favored product (P1) is produced from the most reactive vinyl radical (R1) attacking the most reactive π-bonds (R1 alkene) via the most stereoelectronically favored path (5-exo). Assuming that the radicals can equilibrate prior to the cyclization, this

14 process can be characterized as a kinetic self-sorting of a pool of the four equilibrating radicals via reaction with the lowest activation barrier. In accord with the Curtin–Hammett principle, under the conditions where addition of Sn radicals is reversible, it is not the relative stability of radicals but the absolute energies of the respective cyclization transition states (TSs) that matter.

Scheme 8. Illustration[67] of the proposed radical pool concept for the cyclization of conjugated enynes (energies in kcal/mol).

Literature reports confirm that the addition of vinyl stannanes to double bonds is reversible, confirming that the equilibrium between vinyl radicals is possible.[70–73] For example, Sn radicals are known to isomerize alkenes fast and much faster than Si-based radicals. However, at this point, the “radical pool” is a hypothetical model to fit the observed results. Another explanation for selectivity can be found in a simpler source—kinetic preference for the Sn-radical attack at the propargylic position. The formed vinyl radical from such an attack would provide the appropriate positioning for initiating the cascade. In order to test for the applicability of the two models to the present system, the reactivity of two types of substituted alkynes were compared (Scheme 9) (see Appendix B for additional schemes and analysis) An evaluation of the relative reactivity of the two types of substituted alkynes toward the

HSnBu3/AIBN conditions revealed that the tin radical preferred the “skipped” analog 14a over the unmodified oligoalkyne fragment 15. 15

Scheme 9. Intermolecular competition in radical hydrostannation of alkynes: propargylic ether 14a vs diphenyl acetylene (tolane) 15 (data obtained by coauthor).

Guided by these results, a computational analysis was carried out (see Appendix B). The transition state of SnMe3 radical addition at the propargylic position was found to be relatively low. This quality can be rationalized by considering several interactions between the oxygen lone pairs, the π-system, and the Sn radical. Such transition-state stabilization derives, at least partially, from unusual three-electron interactions between the lone pair of oxygen and the radical orbital at Sn to guide radical attack at the required position.

Scheme 10. Relative free energies of the four vinyl radicals formed by radical attack at the triple bonds of the skipped enediyne 6a at 110°C (energies in kcal/mol, data obtained by coauthor).

16 Additionally, the relative stabilities of the four vinyl radicals that can be formed from the attack of the SnR3 radical on the skipped diyne 6a (A-D) and also a 2c,3e bond between oxygen and tin (E) were compared (Scheme 10). A truncated SnMe3 radical was used. E converged to the most stable vinyl radical A without barrier. The radical intermediate A that corresponds to the experimentally observed pathway was significantly more stable that the other vinyl radicals B-D.

2.2.2 Barriers for the Cyclizations of Vinyl Radicals Cyclization barriers were calculated for the three most stable vinyl radicals (A, B, and D) which can undergo 6-exo-dig and 5-exo-dig cyclizations (see Appendix B). The 13.8 kcal/mol barrier for 6-exo-dig cyclization of the most stable radical A. The next most stable radical D has a barrier of 11.8 kcal/mol. However, when the respective radicals are taken as the reference points, the absolute energy of the 6-exo-dig barrier is lower by ~6 kcal/mol (Scheme 11).

Scheme 11. Comparison of relative energies of the four vinyl radicals and barriers for their exo- dig cyclizations (energies in kcal/mol, data obtained by coauthor).

This difference in absolute barrier energies suggests that the reaction of vinyl radical A will provide the lowest energy path for the escape from the pool (similar to what is seen in Scheme 8) if the barriers for radical equilibrium are sufficiently low. However, because we do not have sufficient information about the barriers for C-Sn bond fragmentation that would allow for the pool of vinyl radicals to be assessed, the kinetic preference for radical A (Scheme 9) and the fast and irreversible 6-exo cyclization is rationalized to be the source of selectivity in this reaction.

17 2.2.3 Full Radical Cascade and Return of the Radical at the β-Carbon

Scheme 12. Proposed mechanism of cascade cyclization.

Scheme 12 shows a proposed mechanism involving an initial formation of a radical intermediate A formed via the attack of the SnBu3 radical at the central alkyne. The subsequent 6- exo-dig cyclization forms the second vinyl radical intermediate F. Attack of the neighboring phenyl π-system results in a delocalized radical G, leading to rearomatization via a 1,5-hydrogen shift.[39] Finally, fragmentation of intermediate H allows for the aromatization of the top ring into a naphthalene moiety. This explanation supports the journey of the radical in this system: it begins with the SnBu3 radical attacking the alkyne position vicinal to the directing group starting a boomerang-like radical journey. The vinyl radical is formed, leading to the 5-exo-dig cyclization: this is the furthest position of the radical from where it started. The formation of the 5-membered ring makes the radical closer to its origins but not enough: another resonance structure can be written. At this point the boomerang is back to its initial position, vicinally to the directing and 18 now leaving group. This position is especially interesting because it will end forming a new π bond and making the directing OR group leave the system. Most importantly, the last step removes the directing group from the product, making this directing approach traceless. The other approach is that G′ can undergo the β-scission of the OR first and then do the 1,5-shift to rearomatize the system. Both possibilities are presented in Scheme 12 and Scheme 13. The proposed reaction mechanism is supported by the calculated free energy profile for the full cascade transformation (Scheme 13). As discussed above, the initial 6-exo-dig cyclization is moderately fast but highly exergonic and effectively irreversible. The mechanism diverges into two pathways at intermediate G′ where the order of the next two steps can be interchanged. The β-scission of the directing -OR group and the alternative pathway where fragmentation precedes 1,5-shift occurring in either order present viable options, both leading to the completion of the reaction.

Scheme 13. Calculated energy profile for the cascade radical transformation of diyne 6a (ΔG and ΔG‡ energies in kcal/mol at 110°C).

19 2.2.4 Functionalization of Stannyl Benzofluorenes Two practical conclusions can be obtained from these results. First, this cascade provides a practical synthetic approach to substituted benzo[a]fluorenes, the class of compounds with known anticancer activity.[74] Furthermore, the Sn-containing products can be introduced in reactions with a variety of electrophiles. For example, they can be readily protodestannylated to yield the respective hydrocarbon and introduced in Stille cross-coupling. Alternatively, they can be converted into an electrophilic benzofluorenone building blocks via reaction with iodine and/or reacted with carbon nucleophiles, i.e., boronic acids under Suzuki conditions (Scheme 14).[75,76]

Scheme 14. Derivatization of benzofluorenes using Stille and Suzuki coupling reactions (data obtained by coauthor).

Additionally, the presence of an activating β-OR group in 17b can be used to direct oxidative dimerization into an expanded polyaromatic system (Scheme 15).

Scheme 15. Oxidative dimerization of 17b (data obtained by coauthor). 20 2.2.5 Formation of Larger Polyaromatic Systems This method of utilizing traceless directing groups in cascade reactions also works with larger systems (Scheme 16). When the oligoalkyne is extended by one alkyne, the success of the expanded cascade is consistent with the higher reaction rate seen in 6-exo-dig cyclizations in similar triyne systems.[25] The remainder of the mechanism proceeds via the same route to form benzofluorenes displayed in Scheme 12.

Scheme 16. Cascade transformation of skipped tris-alkyne 19a (data obtained by coauthor).

The addition of a fourth alkyne also allowed for successful cyclization. However, two diastereomers were detected as a ~1:1 mixture and likely result from the formation of a chiral center and atropoisomerism of the two close naphthalenes in the helicene moiety (Scheme 17).

Scheme 17. Cascade transformation of skipped tetraynes 20a, 21a, and 22a leads to the formation of diastereomeric helicenes (data obtained by coauthor).

21 These structures correspond to the fusion of two different [5]helicenes: one made entirely of benzene rings and the other containing a pentagon. In order to understand the relative influence of the two helicene units at each other, we analyzed the relative energies of the four diastereomers of the parent fused helicene 20b by DFT (Figure 3). The two stable conformations correspond to the same chirality of the two helicenes (either P, P or M, M), so the preferred geometries of the two fused chirality units are strongly coupled. The mismatched isomers are much higher in energy (∼5 kcal/mol and ∼8 kcal/mol higher). On the other hand, effect of chirality at the auxiliary sp3 asymmetric carbon in the two stable stereoisomers is minor (∼0.1 kcal/mol). These computational results are consistent with the experimental observation of two isomeric products formed in the ∼1:1 ratio.[77]

Figure 3. Geometries and energies of the four diastereomeric fused helicenes 20b (only one of the two enantiomers is shown for each structure, ΔG and energies in kcal/mol at 110°C).

2. 2. 6. Selected Photophysical Properties of Benzo[a]fluorene Chromophores The photophysical properties for select compounds were recorded in aerated dichloromethane (see Appendix B).

22 2.3 Conclusion

Polycyclic aromatics are significant subunits in many natural products, pharmaceuticals, and materials.[78–83] The use of alkynes provides for carbon rich starting materials that can be reliably transformed by radical cascade reactions.[14,15,24,84,16–23] Radical cascades also allows for functional group tolerance while maintaining high reactivity and controllable selectivity. In this section, an approach to efficient transformation of skipped oligoalkynes into polycyclic ribbons with an incorporated tin moiety is presented. This group can be used as a handle for regioselective reactions if further functionalization is needed. Regioselectivity of the initial attack is directed by an easily installed methoxy group, which is then eliminated at the completion of the cascade—the methoxy group is truly “traceless” as it is completely removed as the molecule aromatizes. This methoxy directing group is joined by a diverse group of other designs (i.e., carboxylic acids,[85] silanols,[86] pinacolatoboron(B-pin),[87] and nitroso,[88] n-oxide,[89] methyl,[90] PyDipSi,[91] and PyrDipSi,[92,93] methoxyethyl ether[94] groups) used for catalytic C-H activation (Scheme 17) (see Appendix B). However, the design presented in this chapter is unique in that it does not replace a directing group but eliminates it without the need for any additional reaction. This step is an integral part of reaction cascade that provides an efficient approach to Sn-functionalized polyaromatics. Furthermore, our work provides a first example of a traceless directing group in a radical cascade.[95]

23 CHAPTER THREE

RADICAL ALKYNE PERI-ANNULATION REACTIONS FOR THE SYNTHESIS OF FUNCTIONALIZED PHENALENES, BENZANTHRENES, AND OLYMPICENE

Angew. Chem. 2018, 130, 3713–3717

3.1 Introduction

Annulative π-extension (APEX) reactions are useful tools in the creation of polyaromatic nanostructures, such as open nanotubes and graphene nanoribbons.[96–98] Benzannulations—the annealing of additional benzene rings to an existing aromatic system—is a transformation that falls into the APEX category and allows for controlled growth of polyaromatic structures. Alkynes are a great source of high energy carbon content.[20,36,99,100] For example, Scott and co‐workers introduced a Diels–Alder strategy for the growth of a carbon nanotube from the “biphenyl‐like” bay regions, [84,101–103] whereas Swager and co‐workers used acid‐ and electrophile‐promoted alkyne cyclization reactions to anneal additional aromatic rings to paraphenylene polymers.[104,105] Recently, Chalifoux and co‐workers prepared pyrene, peropyrene, and teropyrene derivatives through the benzannulation of alkynes as promoted by Brønsted acids and later expanded this approach to the bottom‐up synthesis of graphene nanoribbons.[106–111] Ito, Itami, and co‐workers reported the Pd/chloranil‐catalyzed annealing of a biphenyl moiety at the K‐region with dibenzosiloles and dibenzogermoles.[98] The armchair region of the polyaromatic units annealed with an alkyne displays the ability of this functionality to serve as “carbon-rich glue” that can connect two carbon nanostructures.[112,113] The scope of this approach is expanding continuously. In particular, alkyne benzannulation at a biphenyl unit was accomplished through electrophile‐assisted,[112,113] transition‐metal‐ catalyzed,[114–121] and oxidative radical pathways.[122] However, these examples are limited to the extension of polycyclic aromatic structures at the armchair edge (bay and “K‐regions”).[123–126] In contrast, alkyne annulations at a zigzag edge (“L‐region”) of carbon nanostructures remain remarkably scarce.[127] A pentagon-free polyaromatic product is possible with such reactions. peri-cyclizations can serve as a potential strategy for terminating exo-dig cascades of oligoalkynes.[26,128–130] This approach is illustrated in Figure 4 c.

The kinetics and thermodynamics of the intramolecular attack of a vinyl radical at a naphthyl or biphenyl core show subtle but important differences. Addition to naphthalene is more

25 favorable thermodynamically owing to lower loss of aromatic stabilization. However, the higher strain in the peri‐cyclization transition state offsets the favorable thermodynamic contribution. The rigidity of a fused bicycle leads to a 2.6 kcal/mol higher activation barrier (corresponding to approximately 100-fold slower cyclization) in comparison to radical attack at the more flexible biphenyl target, which can readily twist to align its aromatic system with the attacking vinyl radical. A unique conceptual difficulty exists for benzannulation at the zigzag edge. The radical product of the “4+2” path in Scheme 18 can be readily converted into a stable phenanthrene moiety through the loss of a single H atom at the ring junction point. But, in the “3+3” path an escape into a stable product is not possible. Even when full conjugation is restored via the loss of HX in the “3+3” product, an odd alternant hydrocarbon, that is, a phenalenyl radical, is created. Although these species are remarkably interesting[131–134] and this new approach to phenalenyl radicals could offer valuable synthetic opportunities, the intrinsic instability associated with the open‐shell structural motif necessitates an additional step that converts initially formed species into stable products.

Scheme 18. Computed kinetics and thermodynamics for intramolecular attack of a vinyl radical at the naphthyl and biphenyl core at the UM06-2X/6-31+G(d,p) level of theory (energies in kcal/mol).

Benzannulation at the peri- position of polyaromatic cores can be performed through

SnBu3‐mediated radical cyclization of propargylic ethers. Depending on the choice of workup

26 (reductive or oxidative), this process furnishes the corresponding tin‐ and iodo‐substituted benzannulated phenalenes and benzanthrones, which can be readily functionalized by classic cross‐coupling approaches.

3.2 Results and Discussion Initial trials of peri-cyclization on the model alkyne 23 were found to proceed most successfully with an HSnBu3 and AIBN reagent combination in toluene (see Appendix C for reagent optimization). The best results were obtained in toluene with 2 equivalents of HSnBu3 and 1 equivalent of AIBN. The directing effect of the -OMe group on the Sn radical to the target position of the alkyne, used before in the preparation of expanded polyaromatics (Figure 4 c.),[128– 130] provided reliable assistance toward the formation of tetracyclic products 24, 25a-Sn, 25b-Sn (Scheme 19).

Scheme 19. Peri-cyclization of 9-anthracenyl propargylic ether in reductive and oxidative regimes (data obtained by coauthors). 27

Scheme 20. Precursors (left), cyclization substrates (center) and products of radical peri- cyclizations (right) (data obtained by coauthors).

The 1H NMR spectra of cyclized product 23 revealed that the -OMe was still present and there was now a CH/CH2 system of allylic protons. In contrast to those reactions in chapters one and two, the fragmentation of the directing group does not occur as readily and will proceed in a slower step to lose methanol to produce benzanthrenes 25a-Sn and 25b-Sn rather than lose a fragmented methoxy radical (Scheme 19). This observation suggests that cyclized radicals are reduced by H-transfer and lose methanol later in a subsequent slower step. Minor amounts of other products were detected from the combination of the cyclized radical and components of reagents and initiators (26). Another set of products was obtained through reaction with additional reagents or through oxidation via purification and exposure to air—benzanthrones (27a-Sn, 27b-Sn, 27a),

28 benzanthrene 25a,[114–117] and iodobenzanthrene 25-I were produced. The large amount of AIBN indicates inefficiency of the radical propagation step, probably owing to the formation of highly stabilized radical intermediates. The scope of the reaction was tested by extending it to other polyaromatic cores. The propargyl ether substrates were prepared from aryl aldehydes or aryl bromides (Scheme 20). [135] Treatment with DDQ and MnO2 provided new polyaromatic ketones in varying yields, whereas TFA gave rise to the destannylated hydrocarbon derivatives.[136,137] Stannylated products are readily converted to iodinated or destannylated products. Of these products, subsequent Stille coupling of the stannanes or Suzuki coupling of the iodo compounds allows for further structural diversification (Scheme 21).

Scheme 21. Protodestannylation (left) and iodination (right) of product 27a-Sn. Cross-coupling approach to extended PAHs (bottom) (data obtained by coauthors).

3.2.1 Computational Analysis Computational analysis indicates that peri‐cyclization in polyaromatics shows relatively small changes for different cyclic cores. Expansion from naphthalene to anthracene has the largest transition‐state‐stabilizing effect (3–5 kcal/mol), whereas the barriers for intramolecular radical

29 attack at phenanthrene and pyrene is predicted to be only about 1 kcal/mol lower relative to that in the naphthalene derivative (Scheme 22). This subject will be explored in detail in the next chapter.

Scheme 22. Computed cyclization barriers and reaction energies at the (U)M06-2X/LanL2DZ level at 110°C in kcal/mol. X = SnMe3.

On the other hand, the progression of intermediate species that evolve under the reaction conditions from the initial cyclized radical provides a complex mechanistic puzzle. We show how this complexity can be unraveled by using the 9‐anthracenyl system as an example. The initially formed cyclic radical G is highly delocalized and potentially can abstract a hydrogen atom at six different carbon atoms to give products A–F (Scheme 23). However, the spin density is concentrated at only three positions. H‐abstraction at these positions is more favorable thermodynamically than abstraction at the remote benzene ring (Scheme 24).

Furthermore, the H-SnMe3 bond dissociation energy (BDE; 71.2 kcal/mol at the same UM06‐2X/LanL2DZ level is less than the calculated BDE for the potentially formed C−H bond in only one of the possible products. The calculated H‐transfer is thermodynamically favorable only for the formation of isomer A (Scheme 23), which we observe experimentally (product 24, Scheme 19). The greater stability of this product is not surprising, considering that it preserves the greatest degree of aromaticity and keeps conjugation with the alkene moiety. 30

However, even the most stable of the initial closed‐shell reduced products, A (Scheme 24), still has two “weak spots”. The first weakness is the tertiary C−H bond; this hydrogen atom may be abstracted by the SnR3 radical (ΔH ≈ −5 kcal/mol) or other transient radicals. This H‐abstraction opens a path to the exergonic loss of an OMe radical with a low energy (ca. 8 kcal/mol) barrier. This step leads to aromatization of the newly formed ring and completes the benzannulation process to form the isolated product 25b-Sn. A parallel pathway suggested by the computational analysis includes aromatization of the initially formed cyclic radical G through the loss of MeOH (Scheme 23, top right). This elimination provides a fully delocalized benzophenalenyl radical H, which can abstract a hydrogen atom to provide another route to products 25a-Sn and 25b-Sn (Scheme 19). The formation of

31 products 26 suggests that the highly delocalized radical H is likely to be persistent under the reaction conditions.[138]

Scheme 24. Relative stabilities of benzanthrene derivatives where X = SnMe3, at (U)M06- 2X/LanL2DZ level at 110°C, in kcal/mol. Experimentally observed products are boxed.

Importantly, a different aromaticity pattern emerges after the loss of MeOH, leading to preferred reactions at the middle ring (position “c”, Scheme 23, top left) as they provide the benzene and naphthalene subunits instead of forming a phenanthrene. The structures of the final aromatized products from both the reductive and the oxidative workup procedures follow this general preference. The same trend displays itself in the cyclization products derived from the other cores (Scheme 20).

32 3.3 Conclusion

In conclusion, peri-cyclizations of acene subunits via vinyl radicals formed from propargylic ethers are useful methods of expanding polyaromatics. Vinyl radicals formed from the attack of Sn at the alkyne moiety provides favorable conditions for benzannulation at the L-region edge of acenes. Initially formed cyclic products can be trapped as and transformed into several varieties of products via both reductive and oxidative pathways with the concomitant loss of the methoxy directing group. Furthermore, the -SnBu3 moiety can be retained or exchanged to give iodoarenes for further cross‐coupling transformations en route to extended polyaromatics.

33 CHAPTER FOUR

ELECTRONIC AND STERIC CONTROL OF RADICAL PERI-CYCLIZATIONS ON ROUTE TO EXPANDED POLYAROMATICS

Submitted for Publication

4.1 Introduction

Benzannulative expansion of polyaromatic systems is an effective method of creating graphene substructures.[20,99,100,106,107,139] The high carbon content and energetic properties of alkynes makes them convenient building blocks for creating expanded cyclic structures (Figure 5).[36,112,113]

Figure 5. Graphene edge types and sites of reactivity with a peri-radical annulation at the zigzag edge.

Success in making graphene ribbons and flakes of the desired sizes and shapes, depends on the absence of structural defects, such as heteroatoms, sp3-hybridized centers, and five- membered rings, can disrupt the perfect honeycomb pattern of graphene fragments. Radical cascades offer an atom-economical approach towards the preparation of functionalized polyaromatics. Earlier, we have reported a number of alkyne-mediated radical cascades initiated via selective attack by a tin radical on the central alkyne of an oligoalkyne precursor.[26,128] The initial attack was followed by a series of 6-exo cyclizations to provide a fully cyclized polyaromatic ribbon. Two structural defects, inherent to the nature of this cascade, have been addressed in a series of design modifications. In particular, the use of skipped, rather than fully conjugated, oligoalkynes allowed to avoid incorporation of a five-membered ring at the

34 initiation point (Figure 6)[45] Formation of a 5-membered cycle at the last C-C bond formation at the end of the cascade can be avoided in two ways: 1) by deactivating the radical to the extent where it is incapable of attacking the terminal aryl ring and the last cyclization is aborted,[129] or 2) by using a cyclization at the peri-position of a naphthalene subunit as the last cycle-forming step.

Because radical peri-cyclizations have been unknown until recently,[140] we explored their viability using several polyaromatic targets with the zigzag edge as partners in the peri-cyclizations with an appropriately positioned vinyl radical. Vinyl radical attack at the peri-position of a polyaromatic target allows for cascade termination with 6-membered cycles. The initially formed products are unstable and the reaction requires either oxidative or reductive termination. For the anthracene substrate, the oxidative workup provides benzo[de]anthracenones (Figure 7). Alternatively, reductive termination produced benzo[de]anthracenes in yields of 56-65%. The purpose of this paper is to use computational analysis to understand the energetics of peri-cyclizations of vinyl radicals, their dependence on the nature of the polyaromatic core as well as on substitution at the radical center and at the propargylic carbon (Figure 7).

Figure 7. An example of peri-cyclization on an anthracene core and the products of oxidative and reductive workups.

4.2 Results and Discussion

Parent examples for the peri- and ortho′-cyclization of naphthalene and biphenyl[122] were examined first to establish a point of reference for expanded systems (Scheme 25). Although a methoxy group cannot be added to the biphenyl substrate to fully resemble the cyclization precursor for the naphthalene system, effect of substitution at the vinyl radical can be compared for both types of cyclizations in order to gain better understanding of electronic factors for the attack at armchair and zigzag edges of a polyaromatic system. These effects were modeled by using an unsubstituted vinyl radical, an α-Ph-substituted radical, and an α-Ph-β-SnMe3- disubstituted radical as the cyclization precursors for both the biphenyl and the naphthalene systems (Scheme 25).

Figure 8. The scope of computational analysis of peri-cyclizations.

36 For all of the cyclization pairs with analogous substitution, the more flexible biphenyl system has a lower transition state despite being less exergonic. This observation suggests that flexibility, or lack thereof, may play a role in the reactivity of the polyaromatic cores. For a more rigid fused naphthalene core, the geometric distortion needed for the radical attack at the π-system is more energetically costly.

Scheme 25. Comparison of substituent effects in the vinyl radical cyclization at peri-position of a. naphthalene and b. ortho′-positions of biphenyl (energies in kcal/mol at 110°C).

4.2.1 Substituent Effects: Direct Substitution at the Alkyne Radical-stabilizing substituents near the vinyl center increase both the activation barriers and reaction energies. For both peri- and ortho′-attack, the presence of a phenyl group at the α- position and then a trimethyl tin at the β-position increased the activation barrier by ~2 kcal/mol overall. The reaction exergonicities decrease even more dramatically by ~15 kcal/mol. In general, peri-cyclizations are slightly less affected by substitution at the vinyl radical than ortho′- cyclizations; and transition states are much less affected by substitution than are the products. The correlation of ΔG and ΔG‡ for the three-substituent combination in each of the cyclization patterns shows that the differences in the activation barrier are due to the radical stabilization effects that decreased exergonicity of the radical attack. Both the α-Ph group and the β-Sn substituent substantially stabilize the reacting radical (Figure 9).[13,141–143]

Figure 9. Correlation of activation (∆G‡) and reaction (∆G) free energies for the two types of cyclizations of polyaromatic systems (energies in kcal/mol at 110°C).

The stabilizing effect of the two substituents is preserved in the transition state as illustrated by where both the C-Sn bond and the Ph group π-systems are aligned well with the attacking radical center.

Figure 10. Transition states of α-Ph-β--disubstituted biphenyl 46b and naphthalene 43b, illustrating the key orbitals interacting with the radical center.

4.2.2 Indirect Substituent Effects: Presence and Orientation of a Methoxy Group at the Propargylic Carbon Due to the essential role of the methoxy group in directing the tin radical attack at the alkyne, we analyzed the cyclization of -OMe-substituted substrates. Remarkably, the outcome of the cyclization depended dramatically on the orientation of the “bystander” propargylic substituents. Considering our long-standing interest in stereoelectronic control of organic reactions,[68,143–151] including the effects of remote substituents,[130,152–154] we have analyzed this situation in more detail as discussed below. 38 The introduction of a methoxy group at the propargyl position leads to interesting effects that depend strongly on the orientation of this substituent (Scheme 26). The activation enthalpy for the transition state 28b is 1.5 kcal/mol lower than for the transition state 43b that lacks the propargylic substituent, whereas the activation barrier for the other transition state (28b-t) is 3.6 kcal/mol higher. Entropic factors change the magnitude of effects slightly but the large (4.3 kcal/mol) influence of remote substituent on the free energy barriers persists. The magnitude of this effect is remarkable for a group that is attached directly neither to the vinyl radical moiety nor to the aromatic target. What makes this observation even more interesting is that the difference in the reaction free energies (1.6 kcal/mol) is significantly smaller than the difference in the activation barriers, indicating that the observed barrier differences may stem from specific transition state stabilization.

39 In the subsequent sections, we expand the list of polyaromatic targets to test whether these stereoelectronic factors are general and operate in the broader family of peri-cyclizations

4.2.3 Effect of the Aromatic Target The expansion of the aromatic system and change in the targeted ring attack leads to noticeable differences in the computed barriers and reaction energies for the radical cyclizations. However, the stereoelectronic effect of the propargylic -OMe group persisted. We will discuss it in the following sections. Herein, we will concentrate our analysis at the lower energy path that leads to the formation of cis-products. It is instructive to compare cyclizations at naphthalene with cyclizations at the two peri-positions of anthracene, at carbons 9 and 1 (Scheme 27). The results are non-trivial – the peri-attack at the anthracene ring can be slower or faster than the attack in the naphthalene system depending on which anthracene ring is targeted. The effects are large. Compared to the cyclization in naphthalene, the free energy of activation is 4.5 kcal/mol lower for the 9th position of anthracene and 1.3 kcal/mol higher for the 1st position of anthracene.

Scheme 27. The vinyl radical cyclization in 1-substituted anthracene 30a and 9-substituted anthracene 23a (energies in kcal/mol at 110°C).

The faster attack at the 9th position (i.e., the central ring) in the 1-substituted anthracene 30a should not be surprising. Two isolated Clar’s sextets are maintained in the product, and their conjugation is possible through the one-carbon bridge. In the second anthracene isomer 23a, attack 40 proceeds at the terminal ring to transform the anthracene moiety into a β-allyl naphthalene 휋- system. It is reasonable to expect this process to be less favored than attack at the central anthracene ring, but it is unclear why it is also less favored than attack at the naphthalene ring of 28a. A closer inspection reveals that part of the problem with the terminal attack in 23a is due to the unfavorable entropic contribution. We will come back to this seemingly anomalous behavior later. Radical additions to the phenanthrenes was analyzed next. Here the results followed the known trends in reactivity of the phenanthrene subunits. Attack at the less aromatic central ring was significantly more exergonic and proceeded via a lower barrier. In particular, when the central double bond is attacked in 1-phenanthrene 34a, the reaction is downhill by 11 kcal/mol (Scheme 28). After the attack, the 휋-system of biphenyl is formed, similar to that for anthracene 23a. Attack at the outer aromatic ring in 32a is less favorable thermodynamically and proceeds through a 3 kcal/mol higher barrier. After the attack, the cyclization product contains an α-allyl naphthalene substructure.

Scheme 28. The vinyl radical cyclization in 1-phenanthrene 34a and 9-phenanthrene 32a structures (energies in kcal/mol at 110°C).

Finally, additions to pyrene generally display trends that are similar to additions to phenanthrenes, reflecting the electronic similarity between the two aromatic systems (Scheme 29). Similar to the phenanthrene example, attack at the weaker central double bond 1-pyrene 36a is more favorable. This process forms a radical that contains phenanthrene, a relatively stable 41 polyaromatic fragment. On the other hand, when the terminal ring of 47a is attacked, the barrier and reaction energy are slightly higher by 1.3 kcal/mol and 1.9 kcal/mol, respectively. A naphthalene and phenalenyl resonance subunits can be discerned in the product of this attack.

Scheme 29. The vinyl radical cyclization in 1-pyrene 36a and 4-pyrene 47a structures (energies in kcal/mol at 110°C).

We have also calculated barriers and reaction energies for the radical cyclizations that yield the trans-products (Scheme 30). Again, the reactions are considerably less favorable kinetically that analogous reactions that yield the cis-products. The only exception is the radical attack at the terminal ring in the reaction of 9-substituted anthracene substrate where the difference in the calculated cis- and trans-activation barriers is very small. However, even in the latter case the trans-product formation remained ~0.1 kcal/mol less favorable kinetically despite being >3 kcal/mol more favorable thermodynamically. This deviation from the general trend in the 9-anthracenes can be attributed to steric interactions that are not present in the other compounds (Figure 11). In both the starting materials and the cis-transition state, the methoxy group is not able to attain the favorable alignment with the C-Sn bond without clashing with the C-H bond at the other peri-position. This unfavorable steric interaction nearly completely compensates for the favorable stereoelectronics of the cis- transition state. As the result, the cis- and trans-peri-cyclizations in the 9-anthracene system have almost identical barriers.

Scheme 30. Calculated reaction free energies and barriers for radical peri-cyclizations that form the trans-products (energies in kcal/mol at 110°C).

Figure 11. Steric effect on the cis-radical attack in the two.

4.2.4 The Role of Aromaticity Considering the well-known role of aromaticity in stability and reactivity of organic molecules,[143][155–161] we have also explored whether the variations in aromatic character of different rings of polycyclic aromatics will have an effect on the reaction energies and barriers of peri-cyclizations (Figure 12). Aromaticity is a complex phenomenon described via an interplay of energetic, structural, and magnetic effects that do not often correlate perfectly with each other. In this work, we chose to use the NICS method developed by Schleyer, et al.[162] as a quantitative indicator of aromaticity. This method was shown to provide valuable information for a variety of aromatic systems in the ground, transition, and excited states.[163–173] NICS(1) values for both faces of each ring in the vinyl radical species were compared. NICS(1) can be used as an indicator of aromaticity[164] as a function of calculating shielding above and below a ring. For the phenanthrene and pyrene pairs of cyclizations that target the same core, but at different positions, the lower barrier correlates to the attack at the less aromatic ring. Additionally, the effect of aromaticity in comparing phenanthrene and pyrene seems to diminish with the increase from three to four rings in the core. Aromaticity in smaller phenanthrene systems had a larger effect on reaction barriers, where the larger pyrene systems had a smaller effect. However, for attack at the anthracene ring system, other factors seem to override this pattern, and the lower barrier is associated with attack at the more aromatic ring. The 1-anthracene reaction is the more facile of the two despite the fact that the stronger ring is broken, and there is a large negative correlation between aromaticity and reaction barrier. This suggests that aromaticity at the site of attack is not an absolute predictor of reaction energies.

45 4.2.5 Stereoelectronic Effects in Peri-cyclizations As the previous part illustrates, the effects of aromaticity can be overridden by other factors. In this section, we show that these observations stem from the stereoelectronic factors associated with the relative position of the -OMe and the -SnR3 group. As we discussed above, the lower energy transition state for the peri-addition to naphthalene has the OCCSn dihedral of 1.4° where the -OMe and C-Sn bonds are syn-periplanar. In contrast, the -OMe and C-Sn bonds are nearly orthogonal in the higher energy transition state. The same trend is observed for all of the other polyaromatic targets. It is appealing to attribute this unexpected but general effect to the clear stereoelectronic differences between the two transition states. In the lower energy transition state, the σC-OMe bond and the radical orbital are aligned with the “relay” C-Sn orbital whereas in the higher energy transition state, the σC-OMe bond is nearly orthogonal to the radical and to the vinyl C-Sn bond. One can suggest that the syn-periplanar arrangement of the C-O and C-Sn bonds can lead to partial electron density transfer from the C-Sn bond,[128] rendering the latter a weaker hyperconjugative donor towards the vinyl radical. In turn, the decreased electron donation to the radical center renders the latter more electrophilic and more reactive towards the electron-rich π-cloud of naphthalene. In the higher energy stereoisomeric transition state, the C-O and C-Sn a nearly orthogonal, so electron density is not drained from the C-Sn bond via σ-conjugation. Instead, the C-Sn bond can fully exert its donor effect on the vinyl radical, deactivating it towards radical attack. An additional deactivating effect that may complement the primary effect discussed above is the alignment of the C-O acceptor with the π-system of the naphthalene. In the higher energy transition state, this alignment can transfer electron density from the naphthalene, rendering the latter less nucleophilic. In this scenario, the C-O bond serves as a stereoelectronic gate: in the lower energy transition state, it deactivates the C-Sn donor and restores electrophilicity of the vinyl radical. In the higher energy transition state, the C-Sn donor lowers electrophilicity of the vinyl radical while the C-O bond lowers nucleophilicity of the π-target. To test for the role of sigma acceptor ability of the propargylic substituent, we have also changed the C-OR group to a C-F bond (Scheme 31). Indeed, the stronger sigma acceptor accentuated the energy difference between the two transition states. The difference now is 3.7

46 kcal/mol. The transition state energy lowering relative to the unsubstituted case illustrates the activating role of these orbital interactions. Adding another acceptor (49a, 50a) is counter-productive – the barriers go up relative to the stereoelectronically aligned systems with a single propargylic substituent. This finding further underscores the stereoelectronic origin of this effect since the second acceptor in the disubstituted systems cannot be aligned properly with the C-Sn bond and the radical center.

Scheme 31. The role of propargylic substituents in reactivity: comparison of C-O and C-F bonds (energies in kcal/mol at 110°C).

Note that we took advantage of the Curtin-Hammett principle and reported the barriers as the energy difference between the lowest energy TS (cis) and the most stable conformer of the reactant (syn). Since the the donor-acceptor interactions in the syn-geometry benefit more from a stronger acceptor (X = F), the difference in the activation barriers is increased by the introduction of a fluorine atom.

47 The stabilization provided by the alignment of -OMe/-F and -SnMe3 partially stems from the σC-Sn → σ*C-X interaction (Table 4). Both the most stable conformer of the reacting vinyl radical and the more stable cis-TS maintain this stabilizing interaction, this effect weakens significantly in the trans-TS (from ~4-5 to ~2 kcal/mol). Unexpectedly, Natural Bond Orbital (NBO) analysis suggests that additional stabilization to the cis-TS comes from the direct through-space donation from the lone pair of oxygen to the σ*Sn-CH3 orbital (~ 3 vs. 0 kcal/mol for cis- vs. trans-). Interestingly, these two donor-acceptor hyperconjugative effects balance density redistribution due to the interaction of O- and Sn-containing moieties in a way that maintains the donor ability of the

C-Sn bond towards the vinyl radical (σC-Sn → vinyl radical interaction) relatively constant. In this NBO description, the geometric changes in the OCCSn system do not considerably perturb the vinyl radical reactivity, modifying the stereoelectronic model suggested earlier.

Table 4. Natural Bond Orbital (NBO) analysis of 28b, 28b-t, 48b, and 48b-t and their corresponding starting materials. Second order perturbation energies for the orbital interactions are given in kcal/mol . Methoxy Fluorine interaction Spin vinyl radical cis-TS trans-TS vinyl radical cis-TS trans-TS α 2.3 2.1 0.9 2.7 2.9 0.9 σ → σ* C-Sn C-X β 2.5 2.1 0.9 2.8 2.9 0.9 α 1.9 1.4 0 1.3 1.3 0 n → σ* X Sn-CH3 β 1.9 1.5 0 1.3 1.3 0 σ → vinyl C-Sn β 31.2 29.0 28.7 29.8 28.8 28.7 radical

4.2.6 Analysis of the 5-membered Cycle Formation Finally, we have evaluated the possibilibity of an alternative cyclization route – the five- membered ring formation by the ortho-attack of the vinyl radical (Scheme 32). The calculated barrier is much higher, suggesting that this process is unlikely to be important from the experimental point of view and explaining why the peri-cyclizations work relatively well. Interestingly, the stereoelectronic preference for the cis-TS is observed for the formation of the 5-membered rings as well. This finding is noteworthy in the naphthalene system where the formation of cis-isomer is ~2 kcal/mol endergonic while the formation of the trans-isomer is thermoneutral. However, the difference in the cis- and trans-cyclization barriers is much lower

48 because attaining the favorable co-planar arrangement of CO and CSn bonds is more difficult in the smaller, more strained five-membered ring. In accord with this notion, the SnCCO dihedral in the cis-TS in the naphthalene system is ~21 degree – a noticeable deviation from coplanarity.

Scheme 32. a. Barriers and reaction energies for 5-membered ring formation in the naphthalene and phenathrene systems. b. Comparison of geometries for the cis- and trans-isomer formation in the naphthalene and phenathrene system (energies in kcal/mol at 110°C).

4.2.7 Comparison of Alkyne and Peri-cyclizations In conclusion, it is interesting to compare the two similar ways for the annealing of two fused rings to the existing cyclic systems shown (Scheme 33). There is a similarity between the two cascades shown there – the initial 6-exo-cyclization makes a new radical that can be potentially trapped by the pendant phenyl group. Alkyne cyclization yield highly reactive vinyl radical that is capable of this addition reaction that affords a new five-membered ring[128,129] whereas the highly delocalized π-radical formed in the peri-cyclization does not undergo the additional C-C bond forming reaction.

Scheme 33. Cascade product variation via alteration of vinyl radical target (energies in kcal/mol at 110°C).

4.3 Conclusion

The theoretical study of peri-cyclization reactions revealed the significance of several factors when using vinyl radicals to expand aromatic systems. In particular, cyclization barriers are consistently lower for the peri-cyclizations that result in six-membered products, especially for those forming cis-products. Formation of the five-membered products from the same radical precursors via an ortho-attack must overcome much higher barriers (~20-25 kcal/mol). These computational results rationalize the preferential formation of the 6-membered products under the experimental conditions. The aromaticity of the attacked ring is important in those cases where it is not masked by the steric factors.

50 The α- and β-substitution and the consequent vinyl radical stabilization have a large effect on reactivity, raising barriers and reaction energies. Introduction of the β-SnMe3 and α-phenyl groups stabilizes the vinyl radical and partially deactivates it towards the cyclization. The key finding is unprecedented sensitivity of the peri-cyclization to the presence and spatial orientation of a “bystander” propargylic -OMe substituent. The two orientations of this substituent give rise to the cis- or trans-isomers of the cyclized product. Stability of these isomers is not dramatically different, and, sometimes, the cis-isomer is less stable. However, in every case the formation of the cis-product proceeds through a significantly (~2-5 kcal/mol) lower barrier than formation of the trans-products, The origin of this unexpected effect is clearly stereoelectronic – in the lower energy transition states, the σC-OMe bond and the radical orbital are aligned with the “relay” C-Sn orbital whereas in the higher energy transition states the σC-OMe bond is nearly orthogonal to the radical and the vinyl C-Sn bond. When the strength of the acceptor was increased by introducing a propargylic C-F bond, even larger effects on the cyclization barriers were observed. This dramatic stereoelectronic effect of a “bystander” group is a conceptually new tool for the control of rate and selectivity of radical reactions.

51 APPENDIX A

CHAPTER ONE SUPPORTING INFORMATION

Experimental Procedure:

Unless otherwise noted, all reactions were carried out under nitrogen atmosphere in oven- dried glassware using standard syringe, cannula, and septa apparatus. Benzene, diethyl ether, toluene, tetrahydrofuran, and hexane were dried with a dry solvent system before use. Dichloromethane was dried over CaH2 before use. Reagents were purchased from commercial sources and used without purification, unless otherwise stated. Reactions were magnetically stirred and monitored by thin layer chromatography carried out on 0.25 mm silica gel plates (60f- 254) using UV light as visualizing agents and ethanolic solution of phosphomolybdic acid and heat as developing agents. Column chromatography was performed using Kieselgel 60 (70-230 mesh) or Kieselgel 60 (230-400 mesh). Preparative thin-layer chromatography (PTLC) separations were carried out on 0.25 or 0.55 mm silica gel plates (60F-254).

Scheme 34. General synthetic scheme for the preparation of 1-(1-(2-iodoethoxy)-3-phenylprop-2- yn-1-yl)-2-(phenylethynyl)benzene.

General Procedure for Synthesis of Substrate (1a): a) Synthesis of 2-(phenylethynyl)benzaldehyde (S-1): 2-bromobenzaldehyde (1.00 g, 5.43 mmol) was added in one portion to a solution of CuI (0.103 g, 10 mol%) in Et3N (30 ml) and degassed with nitrogen for 15 minutes at 23°C. Pd(PPh3)2Cl2 (0.315 g, 5 mol %) was added to the mixture and was stirred for 15 min before being treated with ethynylbenzene (0.630 g, 6.17 mmol) dropwise. The resulting solution was stirred at room temperature for 12 h and then filtered through a celite pad, concentrated, and eluted through a silica column to give the desired 2-(phenylethynyl)benzaldehyde (S-1) (0.93 g, 4.54 mmol, 84%).

52 b) Synthesis of ethyl 2-((3-phenyl-1-(2-(phenylethynyl)phenyl)prop-2-yn-1-yl)oxy)acetate (S- 2): A THF solution of ethynylbenzene (0.63g, 6.17 mmol) was cooled to -78°C n-BuLi (2.5 M in hexane, 2.27 ml, 6.79 mmol) was slowly added to this solution and was stirred for 0.5 h at - 78°C Compound S-1 (1.0 g, 4.86 mmol) was added to the resulting solution and was stirred for 1 h at - 78°C Ethyl bromoacetate (1.0 g, 6.0mmol) was added to the solution and was stirred for 11 h at room temperature. The reaction was quenched with water (15 ml) and extracted with ethyl acetate (100 ml). The extract was washed with brine solution, dried over MgSO4, and concentrated under reduced pressure. The residue was eluted through a silica column to afford compound S-2 (1.39 g, 3.39 mmol, 70%) as pale yellow liquid. c) Synthesis of 2-((3-phenyl-1-(2-(phenylethynyl)phenyl)prop-2-yn-1-yl)oxy)ethanol (S-3): A THF solution of compound S-2 (2.0 g, 5.3 mmol) was cooled to -60°C DIBAL-H (1.0 M in hexane, 7.95 ml, 7.9 mmol) was slowly added to this solution under a nitrogen atmosphere and was stirred for 3h. The reaction was quenched with aq. NH4Cl sol. (20 ml) and extracted with ethyl acetate (100 ml). The extract was washed with brine solution, dried over MgSO4, and concentrated under reduced pressure. The residue was eluted through a silica column to afford 2-((3-phenyl-1- (2-(phenylethynyl)phenyl)prop-2-yn-1-yl)oxy)ethanol S-3 (1.37g, 3.9 mmol, 80%). d) Synthesis of 1-(1-(2-iodoethoxy)-3-phenylprop-2-yn-1-yl)-2-(phenylethynyl)benzene (1a): A DCM solution of compound S-3 (0.5 g, 1.40 mmol) was cooled to 0°C Triphenylphosphine (0.55 g, 2.1 mmol), iodine (0.53 g, 2.1 mmol), and imidazole (0.19 g, 2.8 mmol) were slowly added to this solution and it was stirred at room temperature for 12 h. The reaction was quenched with water and extracted with ethyl acetate (50 ml). The extract was washed with brine solution, dried over MgSO4, and concentrated under reduced pressure. The residue was eluted through a silica column to afford compound 1a (0.59 g, 1.27 mmol, 90%) as yellow liquid.

Scheme 35. Typical procedure for the synthesis of 8-phenyl-2,8-dihydro-1h- benzo[1,2]fluorine[3,4- b]furan.

A toluene solution of 1-(1-(2-iodoethoxy)-3-phenylprop-2-yn-1-yl)-2-(phenylethynyl)benzene (100 mg, 0.216 mmol) was fitted with a condenser and degassed by purging with argon gas. AIBN (10mg, 0.06 mmol) and HSnBu3 (94 mg, 0.32 mmol) were dissolved separately in dry toluene and added slowly to the reaction mixture by using a syringe pump at 110°C, and the reaction was monitored by TLC. After consumption of the starting material, the reaction mixture was allowed 53 to cool to room temperature and filtered through a small celite bed. Solvent was removed under vacuum, and the residue was purified by column chromatography over silica gel, which yielded 8- phenyl-2,8-dihydro-1H-benzo[1,2]fluoreno[3,4- b]furan (1b) (57 mg, 0.17 mmol, 80%).

Spectral data

NMR spectra were recorded on Bruker 600 MHz and Varian 400 MHz instruments and calibrated using residual undeuterated solvents as an internal reference. δ is in ppm, J is the coupling constant and is expressed in Hz. The following abbreviations were used to explain multiplicities: s = singlet, d = doublet, t = triplet, q = quartet, dd = doublet of doublet, m = multiplet, quin = quintuplet, sext = sextet, sep = septet, br = broad. All NMR spectra were run at 600 / 400 MHz (1H NMR) or 150 13 / 100 MHz ( C NMR) in CDCl3 solution.

1-(1-(2-iodoethoxy)-3-phenylprop-2-yn-1-yl)-2-(phenylethynyl)benzene (1a): Pale yellow thick syrup; IR (neat, cm-1): 3090 (m), 3020 (m), 2850 (m), 2150 (m), 1580 (v), 1410 1 (v), 1075 (s), 500 (s); H NMR (400 MHz, CDCl3): δ 7.92 (dd, J = 0.9, 7.7 Hz, 1 H), 7.64- 7.62 (m, 3 H), 7.55-7.52 (m, 2 H), 7.47-7.32 (m, 8 H), 6.04 (s, 1 H), 4.18 – 3.95 (m, 2 H), 3.39 (t, J = 13 7.1 Hz, 2 H), C NMR (100 MHz, CDCl3): δ 139.7, 132.2, 131.7 (2xC), 131.5 (2xC), 128.7, 128.5, 128.4, 128.39, 128.35, 128.2 (2xC), 128.1 (2xC), 127.5, 122.8, 122.3, 122.2, 94.4, 87.5, 86.7, 70.0, 69.8, 2.3; HRMS calcd for C25H19IO: 462.0481; found: 462.0475.

1-(1-(2-iodoethoxy)-3-(4-(trifluoromethyl)phenyl)prop-2-yn-1-yl)-2-(phenylethynyl)benzene (2a): Colorless liquid: IR (neat, cm-1): 3080 (m), 3010 (m), 2860 (m), 2180 (vw), 1520 (m), 1360 (v), 1 1220 (s), 1090 (m), 490 (s); H NMR (400 MHz, CDCl3): δ 7.85 (d, J = 0.9 Hz, 1 H), 7.83- 7.57 (m, 7 H), 7.44-7.36 (m, 5 H), 5.99 (s, 1 H), 4.14-4.07 (m, 1 H), 3.97-3.91 (m, 1 H), 3.36 (t, J = 7.0 13 Hz, 2 H), C NMR (100 MHz, CDCl3): δ 139.4, 132.3, 132.0 (2xC), 131.5(2xC), 128.8, 128.6, 128.5, 128.4 (3xC), 127.4, 126.1 (d, JCF = 10.2 Hz), 125.2 (q, JCF = 247 Hz), 122.8, 122.3, 94.6, 89.0, 86.6, 86.0, 70.0, 69.9, 2.3 (2C merge in other peaks); HRMS calcd for C26H18F3IO: 530.0354; found: 530.0348.

1-(1-(2-iodoethoxy)-3-(4-methoxyphenyl)prop-2-yn-1-yl)-2-(phenylethynyl)benzene (3a): Pale yellow liquid; 3090 (m), 3010 (m), 2850 (m), 2190 (vw), 1580 (m), 1240 (s), 1020 (v), 490 1 (s); H NMR (400 MHz, CDCl3): δ 7.85 (d, J = 7.3 Hz, 1 H), 7.58-7.55 (m, 3 H), 7.44-7.31 (m, 7 H), 6.85-6.80 (m, 2 H), 5.96 (s, 1 H), 4.13-4.05 (m, 1 H), 3.97-3.88 (m, 1 H), 3.79 (s, 3 H), 3.34 13 (t, J = 7.2 Hz, 2 H); C NMR (100 MHz, CDCl3): δ 160.0, 140.2, 133.5 (2xC), 132.5, 131.8 (2xC), 129.0, 128.7, 128.6 (2xC), 127.8, 123.2, 122.6, 114.7, 114.1 (2xC), 94.6, 87.8, 87.1, 85.3, 70.4, 70.1, 55.5, 29.9, 2.6; HRMS calcd for C26H21IO2: 492.0586; found: 492.0579.

4-fluoro-1-(1-(2-iodoethoxy)-3-phenylprop-2-yn-1-yl)-2-(phenylethynyl)benzene (4a): Pale brown liquid; IR (neat, cm-1): 3090 (m), 3010 (m), 2860 (m), 2140 (vw), 1520 (m), 1310 (s), 1 1120 (s), 1090 (m), 500 (s); H NMR (400 MHz, CDCl3): δ 7.88-7.83 (m, 1 H), 7.62-7.59 (m, 2 H), 7.53-7.49 (m, 2 H), 7.41-7.38 (m, 3 H), 7.35-7.27 (m, 4 H), 7.16-7.10 (m, 1 H), 5.95 (s, 1 H), 13 4.17-4.09 (m, 1 H), 3.99-3.91 (m, 1 H), 3.36 (t, J = 7.0 Hz, 2 H); C NMR (100 MHz, CDCl3): δ 162.2 (d, JCF = 246 Hz), 131.7, 131.5 (3xC), 129.5, 129.4 (3xC), 128.8, 128.6 (d, JCF = 29.6 Hz), 128.4 (2xC), 122.3, 122.1, 118.7, 116.0, 115.8, 95.2, 87.7, 86.1, 85.6, 69.8, 69.4, 2.2; HRMS calcd for C25H18FIO: 480.0386; found: 480.0376. 54

4-(3-(2-iodoethoxy)-3-(2-(phenylethynyl)phenyl)prop-1-yn-1-yl)benzonitrile (5a): Brown liquid; IR (neat, cm-1): 3100 (m), 3020 (m), 2860 (m), 2210 (m), 2190 (vw), 1520 (m), 1 1340 (v), 1160 (s), 1060 (m), 500 (s); H NMR (400 MHz, CDCl3): δ 7.79 (d, J = 7.5 Hz, 1 H), 7.60-7.49 (m, 6 H), 7.44-7.32 (m, 6 H), 5.97 (s, 1 H), 4.11-4.03 (m, 1 H), 3.95-3.87 (m, 1 H), 3.33 13 (t, J = 7.0 Hz, 2 H); C NMR (100 MHz, CDCl3): δ 139.04, 132.6, 132.2 (2xC), 132.1 (2xC), 131.8 (2xC), 131.4, 128.8 (2xC), 128.6, 128.3, 127.2, 127.0 122.6, 122.1, 118.1, 111.8, 94.6, 91.0, 86.4, 85.5, 69.9, 69.8, 2.1; HRMS calcd for C26H18INO: 487.0433; found: 487.0429.

8-phenyl-2,8-dihydro-1H-benzo[1,2]fluoreno[3,4-b]furan (1b): Pale brown liquid; IR (neat, cm-1): 3080 (m), 3010 (m), 2870 (s), 1580 (m), 1360 (s), 1120 (s), 700 1 (s); H NMR (400 MHz, CDCl3): δ 7.98 (d, J = 8.16 Hz, 1 H), 7.70 (d, J = 7.52 Hz, 1 H), 7.57 (d, J = 8.3 Hz, 1 H), 7.36-7.32 (m, 4 H), 7.25-7.17 (m, 4 H), 7.10-7.08 (m, 2 H), 5.24 (s, 1 H), 4.93 (t, 13 J = 9.2 Hz, 2 H), 3.80-3.73 (m, 2 H), C NMR (100 MHz, CDCl3): δ 156.7, 150.0, 142.2, 141.0, 136.4, 134.8, 130.0, 128.8 (3xC), 127.9 (2xC), 127.0, 126.6, 126.1, 124.9, 124.7, 124.5, 122.5, 121.0, 120.1, 113.9, 72.1, 53.8, 29.8; HRMS calcd for C25H18O: 334.1358; found: 334.1351.

8-phenyl-10-(trifluoromethyl)-2,8-dihydro-1H-benzo[1,2]fluoreno[3,4-b]furan (2b): White powder; IR (neat, cm-1): 3080 (m), 3010 (m), 2870 (s), 1580 (m), 1360 (s), 1240 (s), 1120 1 (s), 820 (s); H NMR (400 MHz, CDCl3): δ 8.00 (d, J = 8.2 Hz, 1 H), 7.76 (d, J = 8.0 Hz, 1 H), 7.61 (d, J = 8.0 Hz, 1 H), 7.56 (d, J = 8.4 Hz, 1 H), 7.51 (s, 1 H), 7.38-7.35 (m, 1 H), 7.28-7.20 (m, 4 H), 7.08-7.07 (m, 2 H), 5.26 (s, 1 H), 4.97-4.93 (m, 2 H), 3.82-3.72 (m, 2 H), 13C NMR (100 MHz, CDCl3): δ 157.0, 150.2, 144.4, 140.9, 136.1, 134.9, 129.9, 129.0 (2xC), 128.6 (2xC), 127.9, 127.1, 126.4, 125.2, 124.8, 124.5, 122.6, 121.7, 120.9, 120.7, 113.9, 72.2, 53.8, 29.8, (1C merged in other peaks); HRMS calcd for C26H17F3O: 402.1231; found: 402.1224.

10-methoxy-8-phenyl-2,8-dihydro-1H-benzo[1,2]fluoreno[3,4-b]furan (3b): Pale yellow solid; IR (neat, cm-1): 3080 (m), 3010 (s), 2900 (s), 1560 (m), 1350 (s), 1140 (s), 820 1 (s); H NMR (400 MHz, CDCl3): δ 7.95 (d, J = 8.0 Hz, 1 H), 7.59 (d, J = 8.1 Hz, 1 H), 7.52 (d, J = 8.4 Hz, 1 H), 7.31-7.26 (m, 1 H), 7.25-7.14 (m, 4 H), 7.11-7.08 (m, 2 H), 6.90-6.85 (m, 2 H), 5.21 (s, 1 H), 4.92 (t, J = 9.0 Hz, 2 H), 3.83-3.66 (m, 2 H), 3.77 (s, 3 H); 13C NMR (100 MHz, CDCl3): δ 159.5, 156.9, 152.2, 142.6, 136.6, 134.2, 134.1, 130.3, 129.1 (2xC), 128.2 (2xC), 126.9, 126.2, 124.6, 124.2, 122.7, 121.8, 119.7, 113.7, 113.0, 111.4, 72.3, 55.7, 54.1, 30.0; HRMS calcd for C26H20O2: 364.1463; found: 364.1463.

6-fluoro-8-phenyl-2,8-dihydro-1H-benzo[1,2]fluoreno[3,4-b]furan (4b): Pale brown solid; IR (neat, cm-1): 3080 (m), 3010 (m), 2850 (s), 1560 (m), 1350 (s), 1240 (s), 1120 1 (s), 1040 (s), 800 (s); H NMR (400 MHz, CDCl3): δ 7.99-7.95 (m, 1 H), 7.70 (d, J = 7.5 Hz, 1 H), 7.35 (t, J = 7.4 Hz, 1 H), 7.32-7.29 (m, 1 H), 7.25-7.17 (m, 4 H), 7.16-7.13 (m, 1 H), 7.1-7.05 (m, 13 3 H), 5.18 (s, 1 H), 4.93 (t, J = 9.2 Hz, 2 H), 3.81-3.69 (m, 2 H); C NMR (100 MHz, CDCl3): δ 156.9, 150.0, 141.6, 140.7, 137.6, 134.1 (d, JCF = 24.2 Hz), 128.9 (3xC), 127.9 (3xC), 127.1 (2xC), 126.9, 125.0 (2xC), 121.2 (2xC), 117.1, 114.6 (d, JCF = 24.4 Hz), 108.1, 72.0, 53.8, 29.7; HRMS calcd for C25H17FO: 352.1263; found: 352.1264.

55 8-phenyl-2,8-dihydro-1H-benzo[1,2]fluoreno[3,4-b]furan-10-carbonitrile (5b): Pale yellow solid; IR (neat, cm-1): 3080 (m), 3020 (m), 2870 (s), 2230 (m), 1580 (m), 1360 (s), 1 1120 (s), 702 (s); H NMR (400 MHz, CDCl3): δ 8.02 (d, J = 8.01 Hz, 1 H), 7.78 (d, J = 7.9 Hz, 1 H), 7.67-7.65 (m, 1 H), 7.59 (d, J = 8.5 Hz, 1 H), 7.57 (s, 1 H), 7.43-7.39 (m, 1 H), 7.32-7.24 (m, 4 H), 7.10-7.07 (m, 2 H), 5.32 (s, 1 H), 4.99 (d, J = 9.0 Hz, 2 H), 3.86-3.75 (m, 2 H); 13C NMR (100 MHz, CDCl3): δ 157.5, 150.6, 145.7, 140.7, 136.7, 134.9, 131.9, 130.1, 129.4 (2xC), 128.6, 128.0 (2xC), 127.6, 126.9, 125.9, 122.9, 121.6, 121.3, 119.7, 114.1, 109.8, 72.5, 53.9, 31.2, 30.0; HRMS calcd for C26H17NO: 359.1310; found: 359.1310.

Spectra

UV Spectra for compounds 1b and 2b in CH2Cl2:

Acceptor substitution shifts absorbance to the longer wavelengths.

Experimental:

66 Calculated:

X-ray data

Figure 13. X-ray crystal data of compound 3b.

67 Table 5. Crystal data and structure refinement for 3b. Empirical formula C26H20O2 Formula weight 364.42 Temperature 100(2) K Wavelength MoKα, 0.71073 Å Crystal system Monoclinic Space group P 2(1)/c Unit cell dimensions a = 14.040(3) Å α = 90° b = 5.1837(10) Å β = 104.642(4)° c = 25.834(5) Å γ = 90° Volume 1819.2(6) Å3 Z 4 Density (calculated) 1.331 g/cm3 Absorption coefficient 0.083 mm-1 F(000) 768 Crystal size 0.09 x 0.11 x 0.33 mm3 Theta range for data collection 2.48 to 27.30° Index ranges -19≤h≤19, -7≤k≤7, -32≤l≤35 Total reflections 7250 Unique reflections 4045 R(int) 0.0372 Data completeness 98.70% Absorption correction Empirical Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 4045 / 0 / 254 Goodness-of-fit on F2 1.045 Final R indices [I>2sigma(I)] R1 = 0.0745, wR2 = 0.1692 R indices (all data) R1 = 0.1139, wR2 = 0.1909 Diff. peak and hole 0.440 and -0.225 e.Å-3

68 Table 6. Atomic coordinates and equivalent isotropic displacement parameters (Å2) for 3b. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. x y z U(eq) C1 0.22706(17) 0.6747(5) 0.07399(9) 0.0196(5) C2 0.15403(19) 0.4814(5) 0.05687(10) 0.0237(5) C3 0.1289(2) 0.3954(5) 0.00466(11) 0.0298(6) C4 0.1753(2) 0.5011(5) ‐0.03336(10) 0.0295(6) C5 0.24532(19) 0.6891(5) ‐0.01872(10) 0.0266(6) C6 0.27287(17) 0.7805(5) 0.03499(9) 0.0202(5) C7 0.34587(17) 0.9725(5) 0.05263(9) 0.0195(5) C8 0.46086(19) 1.2792(5) 0.04948(9) 0.0244(5) C9 0.44871(18) 1.2778(5) 0.10763(9) 0.0215(5) C10 0.37270(16) 1.0667(5) 0.10402(9) 0.0172(4) C11 0.32729(17) 0.9605(5) 0.14237(9) 0.0179(5) C12 0.25643(17) 0.7701(4) 0.12770(9) 0.0168(4) C13 0.34239(17) 1.0173(5) 0.19961(8) 0.0173(5) C14 0.40189(17) 1.1956(5) 0.23345(9) 0.0205(5) C15 0.39859(17) 1.2132(5) 0.28714(8) 0.0202(5) C16 0.33571(17) 1.0493(5) 0.30650(9) 0.0195(5) C17 0.27664(17) 0.8675(5) 0.27304(9) 0.0190(5) C18 0.27970(16) 0.8539(5) 0.21986(9) 0.0172(5) C19 0.21966(17) 0.6817(5) 0.17551(8) 0.0170(4) C20 0.10956(17) 0.7122(5) 0.17071(9) 0.0184(5) C21 0.0555(2) 0.9126(5) 0.14106(10) 0.0263(5) C22 ‐0.0435(2) 0.9507(5) 0.14031(11) 0.0295(6) C23 ‐0.08839(19) 0.7859(6) 0.16932(10) 0.0284(6) C24 ‐0.0360(2) 0.5839(6) 0.19816(10) 0.0286(6) C25 0.06244(19) 0.5455(5) 0.19868(9) 0.0230(5) C26 0.3700(2) 1.2646(5) 0.39173(9) 0.0277(6) O1 0.39519(13) 1.0844(4) 0.01879(6) 0.0265(4) O2 0.32772(13) 1.0499(4) 0.35880(6) 0.0251(4)

Additional Information

Results provided in this section are part of the published article. This data was primarily produced by, or in collaboration with, a coauthor and is summarized here only as an abbreviated reference. All supporting information for this section is available via the publisher.

69 Table 7. Screening against different reagents, initiators, and solvents.

70 Table 8. Full scope of substrates for radical cascades.

1a 1b

54a 54b

55a 55b

56a 56b

57a 57b

2a 2b

58a 58b

3a 3b

71 Table 8. (Continued).

59a 59b

4a 4b

5a 5b

60a 60b

Figure 14. The ORTEP for 54b and 3b. Probability level 50%. Crystallography provided by Hoa Phan.

72 APPENDIX B

CHAPTER TWO SUPPORTING INFORMATION

Experimental Procedure:

Unless otherwise noted, all reactions were carried out under nitrogen atmosphere in oven-dried glassware using standard syringe, cannula, and septa apparatus. Benzene, diethyl ether, toluene, tetrahydrofuran, and hexane were dried with a dry solvent system before use. Dichloromethane was dried over CaH2 before use. Reagents were purchased from commercial sources and used without purification, unless otherwise stated. Reactions were magnetically stirred and monitored by thin layer chromatography carried out on 0.25 mm silica gel plates (60f-254) using UV light as visualizing agents and ethanolic solution of phosphomolybdic acid and heat as developing agents. Column chromatography was performed using Kieselgel 60 (70-230 mesh) or Kieselgel 60 (230- 400 mesh). Preparative thin-layer chromatography (PTLC) separations were carried out on 0.25 or 0.55 mm silica gel plates (60F-254).

Scheme 36. Synthetic scheme (A1) for the preparation of 1-(1-methoxy-3-phenylprop-2-yn-1- yl)-2-(phenylethynyl)benzene (6a). a) Synthesis of 2-(phenylethynyl)benzaldehyde (S-1) 2-bromobenzaldehyde (1.00 g, 5.43 mmol) was added in one portion to a solution of CuI (0.10 g, 10 mol%) in Et3N (30 mL) and degassed with nitrogen for 15 min at 23°C PdCl2(PPh3)2 (0.32 g, 5 mol %) was added to the mixture and was stirred for 15 min before being treated with ethynylbenzene (0.63 g, 6.2 mmol) dropwise. The resulting solution was stirred at room temperature for 12 h and then filtered through a celite pad, concentrated, and eluted through a silica column to give the desired 2-(phenylethynyl)benzaldehyde (S-1) (0.93 g, 4.5 mmol, 84%). b) Synthesis of 1-(1-methoxy-3-phenylprop-2-yn-1-yl)-2-(phenylethynyl)benzene (1a): A THF solution of ethynylbenzene (0.63 g, 6.2 mmol) was cooled to -78°C n-BuLi (2.5 M in hexane, 2.27 mL, 6.79 mmol) was slowly added to this solution and was stirred for 0.5 h at -78°C 2-(phenylethynyl)benzaldehyde (S-1) (1.00 g, 4.86 mmol) was added to the resulting solution and was stirred for 1 h at -78°C Iodomethane (1.00 g, 6.00 mmol) was added to the solution and was stirred for 12 h at room temperature. The reaction was quenched with water (15 mL) and extracted with ethyl acetate (100 mL). The extract was washed with brine solution, dried over MgSO4, and concentrated under reduced pressure. The residue was eluted through a silica column to afford 1- (1-methoxy-3-phenylprop-2-yn-1-yl)-2-(phenylethynyl)benzene (1a) (1.39 g, 3.39 mmol, 70%) as pale yellow liquid. 73

Scheme 37. Synthetic scheme (A4) for the preparation of oligoalkynes to vary position B- compounds (1o) and (1e). a) Synthesis of 1-(2-(phenylethynyl)phenyl)-3-(trimethylsilyl)prop-2-yn-1-ol (S-5): A THF solution of ethynyltrimethylsilane (0.77 g, 7.8 mmol) was cooled to -78°C n-BuLi (2.5 M in hexane, 3.1 mL, 7.8 mmol) was slowly added to this solution and was stirred for 0.5 h at -78°C 2-(phenylethynyl)benzaldehyde (S-1) (1.32 g, 6.40 mmol) was added to the resulting solution and was stirred for 1 h at -78°C The reaction was quenched with water (15 mL) and extracted with ethyl acetate (60 mL). The extract was washed with brine solution, dried over Na2SO4, and concentrated under reduced pressure. The residue was eluted through a silica column to afford 1- (2-(phenylethynyl)phenyl)-3-(trimethylsilyl)prop-2-yn-1-ol (S-5) (0.95 g, 3.1 mmol, 49%). b) Synthesis of (3-methoxy-3-(2-(phenylethynyl)phenyl)prop-1-yn-1-yl)trimethylsilane (S-6): A THF solution of 1-(2-(phenylethynyl)phenyl)-3-(trimethylsilyl)prop-2-yn-1-ol (S-5) (0.95 g, 3.1 mmol) was cooled to 0°C NaH (60 % wt/wt in oil, 0.15 g, 3.7 mmol) was added to this solution and was stirred for 0.25 h at 0°C Iodomethane (0.48 g, 3.4 mmol) was added to the solution and was stirred at 0°C for 0.5 h. The solution was allowed to warm to room temperature, and was stirred for an additional 3.5 h. The reaction was quenched with water (15 mL) and extracted with ethyl acetate (60 mL). The extract was washed with brine solution, dried over Na2SO4, and concentrated under reduced pressure. The residue was eluted through a silica column to afford (3- methoxy-3-(2-(phenylethynyl)phenyl)prop-1-yn-1-yl)trimethylsilane (S-6) (0.61 g, 1.9 mmol, 67%). c) Synthesis of 1-(1-methoxyprop-2-yn-1-yl)-2-(phenylethynyl)benzene (S-7): To a 3:1 solution of DCM and methanol was added (3-methoxy-3-(2-(phenylethynyl)phenyl)prop- 1-yn-1-yl)trimethylsilane (S-6) (0.23 g, 0.73 mmol) at room temperature. K2CO3 (0.73 g, 5.2 mmol) was added to this solution and was stirred for 2 h at room temperature. The reaction was extracted with ethyl acetate (60 mL). The extract was washed with brine solution, dried over Na2SO4, and concentrated under reduced pressure. The residue was eluted through a silica column to afford compound 1-(1-methoxyprop-2-yn-1-yl)-2-(phenylethynyl)benzene (S-7) (0.13 g, 0.54 mmol, 74%).

74 d) Synthesis of 1-(1-methoxy-3-(4-methoxyphenyl)prop-2-yn-1-yl)-2- (phenylethynyl)benzene (1e): 1-iodo-4-methoxybenzene (0.19 g, 0.82 mmol) was added in one portion to a solution of CuI (0.02 g, 10 mol%) in Et3N (30 mL) and degassed with argon for 15 min at room temperature. PdCl2(PPh3)2 (0.03 g, 5 mol %) was added to the mixture and was stirred for 15 min before being treated with 1-(1-methoxyprop-2-yn-1-yl)-2-(phenylethynyl)benzene (S-7) (0.17 g, 0.67 mmol) dropwise. The resulting solution was stirred at room temperature for 14 h and then filtered through a celite pad, concentrated, and eluted through a silica column to give the desired 1-(1-methoxy-3- (4-methoxyphenyl)prop-2-yn-1-yl)-2-(phenylethynyl)benzene (1e) (0.17 g, 0.48 mmol, 72%) as pale yellow liquid. e) Synthesis of 4-(3-methoxy-3-(2-(phenylethynyl)phenyl)prop-1-yn-1-yl)benzonitrile (1o): Same as 1e using 4-iodobenzonitrile (0.19 g, 0.84 mmol), CuI (0.02 g, 10 mol%), Et3N (30 mL), PdCl2(PPh3)2 (0.03 g, 5 mol %), and 1-(1-methoxyprop-2-yn-1-yl)-2-(phenylethynyl)benzene (S- 7) (0.17 g, 0.70 mmol). Yielded 4-(3-methoxy-3-(2-(phenylethynyl)phenyl)prop-1-yn-1- yl)benzonitrile (1o) (0.16 g, 0.45 mmol, 65%).

Scheme 38. Synthetic scheme (A5) for the preparation of oligoalkynes to vary position C- compound (1h). a) Synthesis of 2-( (trimethylsilyl)ethynyl)benzaldehyde (S-8): 2-bromobenzaldehyde (1 g, 5.4 mmol) was added in one portion to a solution of CuI (0.103 g, 10 mol%) in Et3N (20 mL) and degassed with nitrogen for 20 min at 23°C Pd(PPh3)2Cl2 0.189 g, 5 mol %) was added to the mixture and was stirred for 10 min before being treated with ethynyltrimethylsilane (0.637 g, 6.48 mmol) dropwise. The resulting solution was stirred at room temperature for 12 h and then filtered through a celite pad, concentrated, and eluted through a silica column to give the desired 2-( (trimethylsilyl)ethynyl)benzaldehyde (S-8) (0.875 g, 4.32 mmol, 80%).

75 b) Synthesis of 3-phenyl-1-(2-( (trimethylsilyl)ethynyl)phenyl)prop-2-yn-1-ol (S-9): Same as S-5 using ethynylbenzene (0.13 mL, 1.18 mmol), n-BuLi (2.5 M in hexane, 0.44 mL g, 1.08 mmol), 2-( (trimethylsilyl)ethynyl)benzaldehyde (S-8) (0.2 g, 0.988 mmol). Yielded 3- phenyl-1-(2-( (trimethylsilyl)ethynyl)phenyl)prop-2-yn-1-ol (S-9) (0.259 g, 0.851 mmol, 86%). c) Synthesis of ( (2-(1-methoxy-3-phenylprop-2-yn-1-yl)phenyl)ethynyl)trimethylsilane (S- 10): Same as S-6 using 3-phenyl-1-(2-( (trimethylsilyl)ethynyl)phenyl)prop-2-yn-1-ol (S-9) (0.259 g, 0.851 mmol), NaH (60 % wt/wt in oil, 0.041 g, 1.02 mmol), and iodomethane (0.145 g, 1.02 mmol). Yielded ( (2-(1-methoxy-3-phenylprop-2-yn-1-yl)phenyl)ethynyl)trimethylsilane (S-10) (0.246 g, 0.771 mmol, 78%). d) Synthesis of 1-ethynyl-2-(1-methoxy-3-phenylprop-2-yn-1-yl)benzene (S-11): Same as S-7 using ( (2-(1-methoxy-3-phenylprop-2-yn-1-yl)phenyl)ethynyl)trimethylsilane (S- 10) (0.246 g, 0.771 mmol) and K2CO3 (0.746 g, 5.4 mmol). Yielded 1-ethynyl-2-(1-methoxy-3- phenylprop-2-yn-1-yl)benzene (S-11) (0.188 g, 0.763 mmol, 90%). e) Synthesis of 1-(1-methoxy-3-phenylprop-2-yn-1-yl)-2-( (4-ethoxyphenyl)ethynyl)benzene (1h): Same as 1e using S-11 (0.133 g, 0.539 mmol), CuI (0.010 g, 10 mol%), Et3N (5 mL), PdCl2(PPh3)2 (0.019 g, 5 mol %), and 4-iodoanisole (0.139 g, 0.593 mmol). Yielded Synthesis of 1-(1-methoxy- 3-phenylprop-2-yn-1-yl)-2-( (4-ethoxyphenyl)ethynyl)benzene (1h) (0.168 g, 0.476 mmol, 88%).

Scheme 39. General procedure for the synthesis of 11-phenyl-11h-benzo[a]fluorene (2a).

A toluene solution of 1-(1-methoxy-3-phenylprop-2-yn-1-yl)-2-(phenylethynyl)benzene (1a) (0.10 g, 0.22 mmol) was fitted with a condenser and degassed by purging with argon gas. AIBN (0.01 g, 0.06 mmol) and HSnBu3 (0.09 g, 0.3 mmol) were dissolved separately in dry toluene and added slowly (flow rate 1 mL/hr) to the reaction mixture by using a syringe pump at 110°C, and the reaction was monitored by TLC. After consumption of the starting material, the reaction mixture was allowed to cool down to room temperature and filtered through a small celite bed. Solvent was removed under reduced pressure. The crude reaction mixture was dissolved in 20 mL DCM. Aq. HCl (2 M) (15 mL) was added to above mixture and stirred for 3 h. The reaction mixture was extracted with DCM (30 mL). The extract was washed with brine solution, dried over Na2SO4, and concentrated under reduced pressure. The residue was eluted through a silica column to afford compound purified by column chromatography over silica gel, which yielded 11-phenyl-11H- benzo[a]fluorene (2a) (0.06 g, 0.2 mmol, 86%).

76 Spectral data:

NMR spectra were recorded on Bruker 400 and 600 MHz and Varian 500 MHz instruments and calibrated using residual undeuterated solvents as an internal reference. δ is in ppm, J is the coupling constant and is expressed in Hz. The following abbreviations were used to explain multiplicities: s = singlet, d = doublet, t = triplet, q = quartet, dd = doublet of doublet, m = multiplet, quin = quintuplet, sext = sextet, sep = septet, br = broad. All NMR spectra were run at 600 / 400 1 13 MHz ( H NMR) or 150 / 100 MHz ( C NMR) in CDCl3 solution.

1-(1-methoxy-3-phenylprop-2-yn-1-yl)-2-(phenylethynyl)benzene (1a): Synthetic Scheme A1, 70% yield. Pale yellow thick syrup; IR (neat, cm-1): 3090, 3020, 2850, 2150, 1 1580, 1240, 1075, 700; H NMR (400 MHz, CDCl3): δ 7.84 (dd, J = 1.2 Hz, 6.6 Hz, 1H), 7.60- 7.58 (m, 3 H), 7.51-7.49 (m, 2 H), 7.44-7.31 (m, 8 H), 5.84 (s, 1 H), 3.61 (s, 3 H); 13C NMR (100 MHz, CDCl3): δ 140.1, 132.2, 131.8 (2xCH), 131.5 (2xCH), 128.7, 128.5, 128.4, 128.39 (2xCH), 128.34, 128.2 (2xCH), 127.3, 123.0, 122.5, 122.4, 94.2, 87.2, 86.8, 86.6, 71.6, 56.9; HRMS calcd for C24H18O: 322.1357; found: 323.1363.

1-(1-methoxy-3-(4-methoxyphenyl)prop-2-yn-1-yl)-2-(phenylethynyl)benzene (1e): Synthetic Scheme A4, 72% yield. Pale yellow thick syrup; IR (neat, cm-1): 3060, 2926, 2854, 2220, 1 1605, 1571, 1444, 1509, 1250, 1173; H NMR (600 MHz, CDCl3): δ 7.82 (d, J = 7.8 Hz, 1H), 7.57 (d, J = 7.6, 3H), 7.43-7.39 (m, 3H), 7.38-7.32 (m, 4H), 6.83 (d, J = 8.7 Hz, 2H), 5.79 (s, 1H), 3.81 13 (s, 3H), 3.58 (s, 3H); C NMR (150 MHz, CDCl3): δ 159.7, 140.6, 133.4 (2xCH), 132.3, 131.7 (2xCH), 128.9, 128.6, 128.6 (2xCH), 128.4, 127.6, 123.3, 122.7, 114.9, 114.0 (2xCH), 94.4, 87.4, + 87.1, 85.5, 71.9, 57.1, 55.4; HRMS calcd for C25H20O2: 352.1463; found: [M+NH4] = 370.1804.

1-(hex-1-yn-1-yl)-2-(1-methoxy-3-(4-methoxyphenyl)prop-2-yn-1-yl)benzene (1i): Synthetic Scheme A1, 55% yield. Pale yellow thick syrup; IR (neat, cm-1): 3062, 2925, 2855, 2225, 1 1598, 1571, 1490, 1464, 1189; H NMR (600 MHz, CDCl3): δ 7.75 (d, J = 7.6 Hz, 1 H), 7.48-7.44 (m, 2 H), 7.38 (d, J = 7.6 Hz, 1 H), 7.36-7.23 (m, 5 H), 5.76 (s, 1 H), 3.57 (s, 3 H), 2.51 (t, J = 7.0 Hz, 2 H), 1.68-1.58 (m, 2 H), 1.56-1.46 (m, 2 H), 0.98 (t, J = 7.3 Hz, 3 H); 13C NMR (150 MHz, CDCl3): δ 139.9, 132.1, 131.7 (2xCH), 128.4,128.17 (2xCH),128.15,127.9, 127.2, 123.3, 122.6, 95.5, 87.0, 86.9, 78.0, 71.4, 56.7, 30.8, 22.0, 19.2, 13.6; HRMS calcd for C22H22O: 302.1671; found: [M+NH4]+ = 320.2012.

4-fluoro-1-(1-methoxy-3-phenylprop-2-yn-1-yl)-2-(phenylethynyl)benzene (1k): Synthetic Scheme A1, 41% yield. Pale yellow thick syrup; IR (neat, cm-1): 3061, 2927, 2821, 2217, 1 1606, 1580, 1490, 1444, 1185, 1078; H NMR (400 MHz, CDCl3): δ 7.79 (dd, J = 8.7, 5.8 Hz, 1 H), 7.59-7.55 (m, 2 H), 7.49-7.46 (m, 2 H), 7.38 (t, J = 3.2 Hz, 3 H), 7.34-7.29 (m, 3 H), 7.26 (dd, J = 9.1, 2.8 Hz, 1 H), 7.10 (t, J = 8.5 Hz, 1 H), 5.75 (s, 1 H), 3.58 (s, 3 H); 13C NMR (150 MHz, CDCl3): δ 162.1 (d, JCF = 249.0 Hz), 136.3 (d, JCF = 2.7 Hz), 131.7 (2xCH), 131.6 (2xCH), 129.4, 129.3, 128.8, 128.5, 128.4 (2xCH), 128.2 (2xCH), 124.3 (d, JCF = 9.9 Hz), 122.5 (d, JCF = 19.8 Hz), 118.6 (d, JCF = 23.3 Hz), 116.0 (d, JCF = 21.7 Hz), 95.1, 87.5, 86.4, 85.7 (d, JCF = 2.9 Hz), 71.0, + 56.9; HRMS calcd for C24H17FO: 340.1263; found: [M+NH4] = 358.1610.

1-(1-methoxy-3-(4-(trifluoromethyl)phenyl)prop-2-yn-1-yl)-2-(phenylethynyl)benzene (1n):

77 Synthetic Scheme A4, 73% Yield. Pale yellow thick syrup; IR (neat, cm-1): 3061, 2923, 2853, 1 2223, 1615, 1599, 1490, 1463, 1167, 1272, 1128, 1067; H NMR (400 MHz, CDCl3): δ 7.79 (d, J = 8.1 Hz, 1H), 7.61-7.55 (m, 7 H), 7.43-7.5 (t, J = 7.5 Hz, 1H), 7.40-7.33 (m, 4H), 5.81 (s, 1H), 13 3.60 (s, 3H); C NMR (150 MHz, CDCl3): δ 139.8, 132.3, 132.0 (2xCH), 131.5 (3xCH), 128.9, 128.6, 128.5, 128.4 (3xCH), 128.4, 127.2, 126.4, 125.2 (q, JCF = 7.0 Hz, 3.7 Hz), 123.0, 122.5, + 94.5, 89.4, 86.7, 85.8, 71.5, 57.1; HRMS calcd for C25H17F3O: 390.1231; found: [M+NH4] = 408.1578.

4-(3-methoxy-3-(2-(phenylethynyl)phenyl)prop-1-yn-1-yl)benzonitrile (1o): Synthetic Scheme A4, 65% yield. Pale orange thick syrup; IR (neat, cm-1): 3060, 2930, 2822, 2250, 1 2229, 1603, 1571, 1495, 1446, 1179; H NMR (400 MHz, CDCl3): δ 7.77 (d, J = 8.0 Hz, 1H), 7.61-7.56 (m, 5H), 7.55-7.52 (d, J = 8.7 Hz, 2 H), 7.43 (t, J = 7.3, 1H), 7.40-7.34 (m, 4 H), 5.82 13 (s, 1H), 3.59 (s, 3H); C NMR (100 MHz, CDCl3): δ 139.5, 132.3, 132.2 (2xCH), 131.9 (2xCH), 131.5 (2xCH), 128.8, 128.6, 128.5, 128.4 (2xCH), 127.4, 127.1, 122.9, 122.4, 118.3, 111.8, 94.6, + 91.4, 86.6, 85.4, 71.5, 57.1; HRMS calcd for C25H17NO: 347.1310; found: [M+NH4] = 365.1658.

11-phenyl-11H-benzo[a]fluorene (2a): White solid (m.p.: 198-201°C); IR (neat, cm-1): 3064, 3010, 2870, 1540, 1060, 950; 1H NMR (600 MHz, CDCl3): δ 7.99-7.94 (m, 2 H), 7.91 (d, J = 8.1 Hz, 1 H), 7.85 (d, J = 7.5 Hz, 1 H), 7.67 (d, J = 8.2 Hz, 1 H), 7.41-7.37 (m, 2 H), 7.35-7.31 (m, 2 H), 7.27-7.21 (m, 4 H), 7.13-7.12 (m, 2 H), 13 5.35 (s, 1 H); C NMR (150 MHz, CDCl3): δ 149.1, 142.6, 141.6, 140.9, 139.3, 133.5, 130.4, 129.0, 128.9 (2xC), 128.8, 128.0 (2xCH), 127.1, 126.9, 126.7, 126.3, 125.1, 124.9, 124.6, 119.6, 118.5, 54.0; HRMS calcd for C23H16: 292.1252; found: 292.1247.

9-methoxy-11-phenyl-11H-benzo[a]fluorene (2e): Pale orange solid (m.p.: 162-163°C); IR (neat, cm-1): 3057, 2925, 2852, 1600, 1581, 1483, 1454, 1 1286; H NMR (400 MHz, CDCl3): δ 7.94-7.88 (m, 2 H), 7.87 (d, J = 7.1 Hz, 1 H), 7.72 (d, J = 8.2 Hz, 1 H), 7.62 (d, J = 8.2 Hz, 1 H), 7.35 (t, J = 7.4 Hz, 1 H), 7.32-7.20 (m, 4 H), 7.12 (d, J = 7.2 Hz, 2 H), 6.92 (d, J = 8.4 Hz, 1 H), 6.88 (s, 1H), 5.30 (s, 1H), 3.79 (s, 3H); 13C NMR (150 MHz, CDCl3): δ 159.5, 151.0, 141.8, 141.7, 139.3, 134.0, 132.9, 130.4, 128.93 (2xCH), 128.91, 128.8 (2xCH), 128.0, 126.8, 126.3, 124.7, 124.3, 120.3, 118.2, 112.9, 111.0, 55.5, 54.1; HRMS calcd for C24H18O: 322.1358; found: 322.1350.

11-butyl-11H-benzo[a]fluorene (2i): Pale yellow liquid; IR (neat, cm-1): 3052, 2923, 2854, 1607, 1583, 1523, 1467; 1H NMR (400 MHz, CDCl3): δ 8.11 (d, J = 8.7 Hz, 1 H), 7.94 (d, J = 8.7 Hz, 1 H), 7.91 (d, J = 8.6 Hz, 1 H), 7.87 (d, J = 8.6 Hz, 1 H), 7.81 (d, J = 7.9 Hz, 1 H), 7.61 (d, J = 7.6 Hz, 1 H), 7.56 (t, J = 7.6 Hz, 1 H), 7.47 (t, J = 7.5 Hz, 1 H), 7.41 (t, J = 7.1 Hz, 1 H), 7.33 (t, J = 7.4 Hz, 1 H), 4.45-4.41 (m, 1H), 2.43-2.33 (m, 1H), 2.24-2.12 (m, 1H), 1.25-1.06 (m, 2 H), 0.94-0.83 (m, 2 H), 0.71 (t, J = 7.3 Hz, 13 3 H); C NMR (150 MHz, CDCl3): δ 148.5, 143.0, 141.8, 138.5, 133.3, 130.4, 129.2, 128.0, 126.8, 126.3, 126.2, 125.0, 124.0 (2xCH), 119.5, 118.6, 47.1, 33.2, 26.8, 22.9, 13.8; HRMS calcd for C21H20: 272.1565; found: 272.1565.

2-fluoro-11-phenyl-11H-benzo[a]fluorene (2k): White solid (m.p.: 160-162°C); IR (neat, cm-1): 3059, 2922, 2851, 1630, 1592, 1493, 1474, 1072; 1 H NMR (400 MHz, CDCl3): δ 7.92 (s, 2 H), 7.88 (dd, J = 9.0, 5.8 Hz, 1 H), 7.84 (d, J = 7.6, 1 H),

78 7.39 (t, J = 7.1 Hz, 1 H), 7.33 (d, J = 7.5 Hz, 1 H), 7.29-7.21 (m, 5 H), 7.15 (t, 8.7 Hz, 1 H), 7.12- 13 7.08 (m, 2 H), 5.29 (s, 1 H); C NMR (150 MHz, CDCl3): δ 149.2, 141.0, 140.5 (d, JCF = 51.7 Hz), 131.4, 131.3, 131.3, 130.5 (3xCH), 129.0, 128.8 (2xCH), 128.0, 127.3, 127.3, 127.0, 125.0, 119.9, 117.8, 115.5, 115.4, 108.0 (d, JCF = 21.7 Hz), 54.1; HRMS calcd for C23H15F: 310.1158; found: [M+NH4]+ = 328.1496.

11-phenyl-9-(trifluoromethyl)-11H-benzo[a]fluorene (2n): Pale yellow solid (m.p.: 175-179°C); IR (neat, cm-1): 3060, 2921, 2851, 1617, 1599, 1492, 1445, 1 1168, 1123, 1084; H NMR (400 MHz, CDCl3): δ 8.00 (s, 2 H), 7.92 (dd, J = 8.1, 4.0 Hz, 2 H), 7.66 (t, J = 7.5 Hz, 2 H), 7.55 (s, 1 H), 7.43 (t, J = 7.5 Hz, 1 H), 7.35 (t, J = 7.5 Hz, 1 H), 7.30-7.24 13 (m, 3 H), 7.11 (d, J = 7.2 Hz, 2 H), 5.39 (s, 1 H); C NMR (100 MHz, CDCl3): δ149.3, 144.5, 143.9, 140.4, 137.8, 134.0, 130.2, 129.3 (2xCH), 129.1 (2xCH), 129.0, 128.0 (2xCH), 127.2, 126.7, 125.9, 124.8, 124.68, 124.66, 121.8 (2xC), 119.7, 118.6, 54.1; HRMS calcd for C24H15F3: 360.1126; found: 360.1124. White solid (m.p.: 183-185°C); IR (neat, cm-1): 3059, 2925, 2853, 1 2225, 1607, 1492, 1472, 1451; H NMR (400 MHz, CDCl3): δ 7.98 (q, J = 8.5, 8.0 Hz, 2 H), 7.93 (d, J = 8.1 Hz, 1 H), 7.88 (d, J = 7.8 Hz, 1 H), 7.66 (t, J = 8.6 Hz, 2 H), 7.57 (s, 1H), 7.46 (t, J = 7.1 Hz 1 H), 7.36 (t, J = 7.4 Hz 1 H), 7.29-7.26 (m, 3 H), 7.08 (d, J = 6.4 Hz 2 H), 5.36 (s, 1 H); 13 C NMR (100 MHz, CDCl3): δ 149.4, 145.5, 144.2, 139.8, 137.5, 134.2, 131.7, 130.0 (2xC), 129.5 (2xCH), 129.2, 129.0, 128.5 (2xCH), 127.8, 127.4, 126.9, 126.3, 124.8, 120.1, 118.5, 109.7, 53.9; HRMS calcd for C24H15N: 317.1204; found: 317.1196.

1-(1-methoxy-3-phenylprop-2-yn-1-yl)-2-(phenylethynyl)benzene (1a)

1-(1-methoxy-3-(4-methoxyphenyl)prop-2-yn-1-yl)-2-(phenylethynyl)benzene (1e)

4-fluoro-2-(1-methoxy-3-phenylprop-2-yn-1-yl)-1-(phenylethynyl)benzene (1i)

4-fluoro-1-(1-methoxy-3-phenylprop-2-yn-1-yl)-2-(phenylethynyl)benzene (1k)

1-(1-methoxy-3-(4-(trifluoromethyl)phenyl)prop-2-yn-1-yl)-2-(phenylethynyl)benzene (1n)

83 1-(1-methoxy-3-(4-(trifluoromethyl)phenyl)prop-2-yn-1-yl)-2-(phenylethynyl)benzene (1n)

4-(3-methoxy-3-(2-(phenylethynyl)phenyl)prop-1-yn-1-yl)benzonitrile (1o)

11-phenyl-11H-benzo[a]fluorene (2a)

9-methoxy-11-phenyl-11H-benzo[a]fluorene (2e)

11-butyl-11H-benzo[a]fluorene (2i)

2-fluoro-11-phenyl-11H-benzo[a]fluorene (2k)

11-phenyl-9-(trifluoromethyl)-11H-benzo[a]fluorene (2n)

11-phenyl-11H-benzo[a]fluorene-9-carbonitrile (2o)

Computational Details

General Information

All calculations were performed using the software package Gaussian ’09 and NBO 3.0 included in this same package. The methods used were UB3LYP and UM06-2X and the basis set was LanL2DZ. The methods used for fused helicene optimization was B3LYP/6- 31G(d). B3LYP/6-31G(d) optimized structures and HF energies in gas phase: fused helicene 2v (M, M) C 0.000000326 0.000000805 0.000000202 HF= -1500.6581608 hartree C -0.000000297 -0.000000231 0.000000934 C -0.000000221 0.000000006 0.000002155 C 0.000000320 -0.000000288 0.000002130 C 0.000000279 0.000000309 0.000001828 C -0.000000065 -0.000000197 0.000000137 C 0.000000633 -0.000000165 0.000000968 C -0.000000344 -0.000000374 0.000002261 C 0.000000080 -0.000000641 0.000002565 C -0.000000021 -0.000000246 0.000002835 C -0.000000248 -0.000000816 0.000003874 C 0.000000321 -0.000000915 0.000004200 C 0.000000073 -0.000000378 0.000003841 C -0.000000631 -0.000001103 -0.000000372 C -0.000000503 -0.000000968 -0.000000848 C 0.000000015 0.000000659 -0.000000888 C -0.000000922 -0.000000990 -0.000001116 C 0.000000277 0.000000680 -0.000001295 C -0.000001524 -0.000001811 -0.000001610 C -0.000000017 0.000000563 -0.000000572 C -0.000001009 -0.000001861 -0.000002188 C 0.000000292 0.000000123 0.000000305 C -0.000000851 -0.000000854 -0.000002097 C 0.000000094 0.000000069 0.000000648 H -0.000000004 0.000000411 -0.000000583 91 H -0.000000084 0.000000323 -0.000000763 C 0.000000783 -0.000001547 -0.000001352 H -0.000000138 0.000000158 -0.000000257 C 0.000000358 0.000000798 -0.000000379 H 0.000000049 0.000000242 0.000000060 C -0.000001567 0.000000288 -0.000000792 H 0.000000131 -0.000000125 0.000001296 C -0.000001935 -0.000001170 -0.000000628 H 0.000000104 0.000000037 0.000000708 C -0.000001732 -0.000000719 0.000001241 H -0.000000080 -0.000000189 0.000001001 C -0.000000694 -0.000000421 0.000001021 H 0.000000057 -0.000000323 0.000001767 C -0.000000174 0.000002949 0.000001755 H 0.000000099 -0.000000357 0.000002026 H -0.000000091 -0.000000238 0.000000405 H 0.000000030 -0.000000205 0.000001515 H -0.000000332 -0.000000094 0.000000465 H -0.000000396 -0.000000520 -0.000000090 H 0.000001347 -0.000000174 0.000001067 H -0.000000547 -0.000000772 -0.000000719 H 0.000000021 -0.000000707 0.000000110 H -0.000000641 -0.000000698 -0.000001078 H -0.000000369 -0.000000070 -0.000000868 H -0.000000525 -0.000000418 -0.000000849 H 0.000000052 -0.000000731 -0.000000202 C -0.000000440 -0.000000343 -0.000000065 H 0.000000829 0.000000613 -0.000000516 C -0.000000127 0.000000243 -0.000001106 H 0.000000695 -0.000000010 -0.000000560 C -0.000002059 0.000000335 -0.000001569 H 0.000000262 -0.000000826 -0.000001156 C -0.000000674 -0.000000690 0.000000602 H 0.000001036 -0.000001263 -0.000000907 C 0.000000228 0.000000267 0.000000831 H -0.000001612 -0.000001151 0.000000055 C 0.000000585 0.000000066 0.000000119 H -0.000000384 -0.000000511 0.000001149 H -0.000000325 -0.000000595 -0.000000378 H -0.000000219 0.000000036 0.000000608 C 0.000000533 0.000001143 0.000001378 H -0.000002393 0.000001450 0.000000484 C 0.000001343 0.000001281 0.000001620 C -0.000000625 0.000000369 -0.000005779 C 0.000000356 0.000001003 0.000000917 C 0.000007237 -0.000002350 0.000015495 C 0.000000146 0.000000779 -0.000000352 C -0.000001088 -0.000000772 -0.000002062 C 0.000001643 0.000000432 -0.000002947 C -0.000001003 -0.000001842 -0.000001501 C 0.000001658 -0.000000355 -0.000003072 C -0.000001051 0.000002344 -0.000000374 C -0.000000973 0.000000406 -0.000004481 C -0.000001574 0.000002627 -0.000002081 C 0.000000285 0.000002128 -0.000003436 H -0.000003928 -0.000000365 -0.000003144 C 0.000001514 0.000000889 -0.000004251 C 0.000002411 0.000000805 0.000000454 H -0.000000418 0.000000595 -0.000000462 C 0.000000633 0.000001475 -0.000000629 H 0.000000848 0.000000769 -0.000001525 C 0.000001422 0.000002112 -0.000000886 H 0.000000533 0.000000793 -0.000002415 C 0.000000162 0.000001705 -0.000001551 H -0.000000687 -0.000000186 -0.000001212 C -0.000000192 0.000000811 -0.000000622 H 0.000000555 -0.000000054 -0.000002180 C 0.000000571 0.000002186 -0.000000032 H 0.000000540 0.000000521 0.000001022 C -0.000000401 0.000002173 -0.000000819 H 0.000000460 0.000000797 0.000000870 C 0.000001659 0.000001273 0.000000838 H 0.000000361 0.000000651 0.000000369 C -0.000001264 0.000000121 0.000001954 H 0.000000002 0.000000188 -0.000000211 H -0.000000199 0.000000282 0.000000283 H -0.000000105 0.000000613 0.000000481 fused helicene 2v (P, P) H -0.000000352 0.000001079 0.000000514 HF= -1500.6579929 H -0.000000398 0.000000879 0.000000124 H -0.000000363 0.000001014 0.000000209 H 0.000000228 0.000000098 -0.000000563 H 0.000000335 0.000000470 -0.000000158 H 0.000000801 0.000000603 0.000000369 H 0.000000204 0.000000888 0.000000657

fused helicene 2v (P, M) HF= -1500.6487608

C -0.000000955 -0.000000806 0.000000919 C -0.000000077 -0.000000673 0.000000569 C -0.000000345 -0.000000314 0.000002613 C 0.000000044 -0.000000173 0.000000063 C 0.000000455 -0.000000863 0.000000573 C -0.000000474 -0.000001336 -0.000000364 C 0.000001131 0.000000714 -0.000000025 C -0.000000802 -0.000002490 -0.000001390 C -0.000000278 -0.000001532 -0.000000905 C -5.620526 -3.050870 -0.807159 C 0.000000439 -0.000002120 -0.000000041 C -4.366347 -3.046546 -1.454918 C -0.000002970 -0.000002814 0.000000732 C -3.412460 -2.103373 -1.132837 C 0.000004059 -0.000000032 0.000001513 C -3.659571 -1.100945 -0.156023 C -0.000000079 0.000000218 -0.000000022 C -4.970832 -1.049540 0.414219 C 0.000000947 -0.000000499 -0.000001505 C -5.914821 -2.061295 0.104922 C 0.000000104 0.000000293 -0.000002184 C -2.694174 -0.068311 0.183796 C 0.000000687 -0.000000972 -0.000001169 C -3.201963 1.138450 0.707784 C 0.000001111 -0.000001704 -0.000001552 C -4.500167 1.148474 1.304305 92 C -5.327596 0.064946 1.226586 C -1.246692 -0.175952 -0.022365 C -5.482849 -2.956634 0.969078 C -0.489509 1.009129 -0.186396 C -4.104860 -3.151154 1.204758 C -1.194063 2.289259 -0.179348 C -3.187737 -2.183219 0.850452 C -2.463121 2.369152 0.458163 C -3.593268 -0.959359 0.252457 C -0.696587 3.442993 -0.821620 C -4.998867 -0.730355 0.115737 C -1.334281 4.667428 -0.709247 C -5.917000 -1.760656 0.440975 C -2.505838 4.774383 0.054695 C -2.661087 0.098968 -0.101981 C -3.068149 3.637820 0.609229 C -3.171800 1.412013 -0.169229 C -0.557074 -1.455287 0.035938 C -4.576832 1.606093 -0.342187 C 0.796672 -1.545618 -0.424628 C -5.453504 0.561489 -0.276527 C -1.131372 -2.631031 0.589282 C -1.230808 -0.100581 -0.347780 C -0.489347 -3.850189 0.528781 C -0.343393 0.985333 -0.147886 C 0.769153 -3.960051 -0.097627 C -0.891784 2.256626 0.314997 C 1.405946 -2.824830 -0.546735 C -2.274364 2.524180 0.112760 H -6.358161 -3.810264 -1.051863 C -0.118937 3.218212 1.000789 H -4.150187 -3.787405 -2.219904 C -0.635683 4.457848 1.337889 H -2.462688 -2.110549 -1.653351 C -1.960058 4.774870 1.000316 H -6.894293 -2.017022 0.575577 C -2.767026 3.814112 0.416715 H -4.832269 2.031804 1.838700 C -0.714432 -1.347681 -0.894398 H -6.302055 0.077360 1.708534 C 0.694275 -1.592495 -0.862831 H 0.197991 3.364039 -1.426296 C -1.523482 -2.319106 -1.542234 H -0.929356 5.537748 -1.218348 C -1.001901 -3.515625 -1.989784 H -3.002398 5.734406 0.166581 C 0.365678 -3.810029 -1.810266 H -4.027030 3.722336 1.108017 C 1.199791 -2.855920 -1.271423 H -2.094636 -2.570578 1.077377 H -6.196202 -3.732682 1.232780 H -0.958795 -4.727145 0.966073 H -3.760936 -4.067679 1.676431 H 1.255611 -4.927972 -0.182741 H -2.137171 -2.348975 1.054593 H 2.407018 -2.894998 -0.954868 H -6.978700 -1.571736 0.299797 C 1.522144 -0.335059 -0.597536 H -4.954678 2.602897 -0.540859 C 3.005304 -0.190170 -0.924502 H -6.516904 0.721197 -0.436747 C 3.995376 -1.062695 -0.160711 H 0.897845 2.973507 1.281045 C 0.940069 0.901977 -0.345586 H -0.017429 5.176416 1.868960 C 2.035327 1.906237 -0.247708 H -2.369428 5.751730 1.242909 C 3.236676 1.284615 -0.643249 H -3.814093 4.043438 0.254727 H 3.141948 -0.394720 -1.998075 H -2.573169 -2.113606 -1.703734 C 2.093617 3.214479 0.254948 H -1.650926 -4.230855 -2.487575 C 3.312738 3.895316 0.268146 H 0.765867 -4.767045 -2.134067 C 4.481416 3.290951 -0.202251 H 2.263920 -3.049118 -1.184068 C 4.447295 1.966284 -0.644769 C 1.555008 -0.496058 -0.591226 C 3.927161 -1.181140 1.234604 C 3.069011 -0.507411 -0.710552 C 5.028526 -1.719470 -0.839289 C 3.800893 -1.267840 0.392979 C 5.970716 -2.483397 -0.144994 C 1.062534 0.788411 -0.409925 C 4.863823 -1.943611 1.929031 C 2.195628 1.733272 -0.631088 C 5.890248 -2.598434 1.242038 C 3.380434 0.977128 -0.755919 H 3.131149 -0.676028 1.775091 H 3.363342 -0.954053 -1.670523 H 4.792840 -2.028055 3.010339 C 2.259163 3.114867 -0.860775 H 6.619070 -3.193721 1.785500 C 3.494159 3.716278 -1.117137 H 5.095109 -1.636692 -1.922362 C 4.669955 2.963336 -1.153793 H 6.763671 -2.987911 -0.691082 C 4.611481 1.577067 -0.983247 H 1.211494 3.702914 0.648237 C 3.484911 -1.063754 1.743545 H 3.348473 4.909123 0.658441 C 4.830145 -2.160871 0.073031 H 5.420596 3.837393 -0.192357 C 5.529730 -2.837447 1.075739 H 5.360594 1.461451 -0.949030 C 4.180271 -1.737905 2.745367 C 5.206161 -2.628100 2.415502 fused helicene 2v (M, P) H 2.687013 -0.374663 2.006981 HF= -1500.6512057 H 3.920379 -1.569268 3.787237 H 5.746329 -3.154240 3.197988 H 5.087157 -2.329932 -0.970826 H 6.324720 -3.528016 0.806316 H 1.365352 3.725390 -0.857248 H 3.533940 4.788259 -1.292235 H 5.623720 3.449300 -1.340726 H 5.512728 0.972325 -1.048539

93 Additional Information

Table 9. Full scope of 1-(2-alkynylphenyl)propargyl methyl ethers.

94 Table 10. Optimization of reaction conditions.

Table 11. Further optimization of SnBu3 addition to alkyne 1a.

95 Table 12. Full scope of radical cascade of propargyl methyl ethers.

Figure 15. ORTEP diagram for 2a.

Figure 16. ORTEP diagram for 2p-Sn.

Scheme 40. Selected electronic interactions (NBO analysis in kcal/mol) contributing to the structure and stability of the transition state of the SnMe3 radical additions to the bis-alkyne 1a to form the most stable radical A.a

Figure 17. Calculated geometries of the four vinyl radicals A-D at the UM06-2X/LanL2DZ level of theory.

Scheme 41. Selected electronic interactions (NBO energies in kcal/mol) contributing to the structure and stability of three vinyl radicals A, C, and D.a

Figure 18. Geometries of radical A and its TS for the 6-exo-dig cyclization.

Figure 19. Geometries of radical D and its TS for the 5-exo-dig cyclization.

Figure 20. Geometries of radical B and its TS for the 5-exo-dig cyclization.

99 Table 13. Photophysical properties of select complexes in CH2Cl2.

Figure 21. Normalized (a) absorption and (b) emission spectra of 2a, 2c, 2o, and 2q in CH2Cl2 at room temperature. The absorption spectra have been normalized with respect to absorption at 316 nm.

100

Figure 22. Normalized (a) absorption and (b) emission spectra of 2a, 2u, and 8 in CH2Cl2 at room temperature. The absorption spectra have been normalized with respect to absorption at 316 nm.

101 APPENDIX C

CHAPTER THREE SUPPORTING INFORMATION

Computational Data

panth_Vrad_d_2: C -1.44454500 0.53292600 0.86763200 E = -539.8072333 C -2.85516000 0.52310000 0.84225900 C -3.53331300 -0.35855500 0.01235200 H -3.35582100 -1.97854000 -1.40137900 H -0.87339300 -2.03035200 -1.30477900 H -0.93375600 1.04762200 1.67724200 H -3.40562700 1.21676300 1.47047700 H -4.61844100 -0.34401600 -0.02241200 C 2.89868700 -1.50418500 0.30963100 C 3.55110600 -0.30173200 0.04414000 C 2.80661100 0.84856200 -0.19871000 C 1.40800500 0.82939800 -0.16283100 C 0.75001500 -0.38908100 0.11558000 C 1.50652400 -1.54237300 0.33751600 0 2 H 3.46931600 -2.40840300 0.49663600 H 4.63548500 -0.26111500 0.01860800 C -3.3557650000 -2.9479680000 0.9179780000 H 3.31353400 1.78265600 -0.42791800 H 0.98914400 -2.47398800 0.55091600 C 0.65914500 2.06018400 -0.49639700 C 3.12386400 -0.93375700 0.77984100 H 1.24652400 2.84420600 -0.98549700 C 1.73847600 -1.08133800 0.78728400 C -0.62854400 2.25985600 -0.26580800 C 0.93021300 -0.28475500 -0.03301100 H -1.28419800 3.09729100 -0.47490500 C 1.54273500 0.65814200 -0.86826900 C 2.92756400 0.80449700 -0.87829900 panth_rad_2: C 3.72252200 0.01014400 -0.05233500 E = -539.8487162 H 3.73558700 -1.55394500 1.42785100 H 1.27167100 -1.80897400 1.44586200 H 0.92487300 1.26882300 -1.52131200 H 3.38623700 1.53550700 -1.53712400 H 4.80182300 0.12557900 -0.05934900 C -2.42387800 -1.99718700 -0.31826600 C -3.31307300 -0.93507600 -0.15082000 C -2.82329600 0.34229800 0.08401100

C -1.44511200 0.59459400 0.14476900 0 2 C -0.54625500 -0.47436700 -0.04200800 C 2.81806600 -1.56269500 -0.28059600 C -1.05528900 -1.76144900 -0.26212000 C 1.42155100 -1.57592100 -0.20138600 H -2.79530700 -3.00141300 -0.49674900 C 0.69225400 -0.43919800 0.09914500 H -4.38432000 -1.10565400 -0.19121000 C 1.41122900 0.82796000 0.49859300 H -3.50919200 1.16916300 0.24716600 C 2.87979900 0.81013900 0.18818400 H -0.35576500 -2.57853600 -0.41592200 C 3.53077100 -0.33493800 -0.13098100 C -0.96614200 1.96137200 0.45327100 H 3.35342100 -2.46934300 -0.53862300 H 0.05557200 2.04707600 0.83422500 H 0.89589800 -2.49404400 -0.44785700 C -1.68025700 3.06142800 0.31727600 H 1.33065900 0.88772200 1.61148500 H -1.52361000 4.11509300 0.49861900 H 3.41810900 1.75034100 0.27937500 H 4.60225300 -0.31896200 -0.30733800 panth_rad_TS_VrAtt_2: C -2.94914900 -1.46959900 0.14163400 E = -539.7957341 C -3.57649800 -0.23546300 -0.05088800 C -2.80442600 0.91311400 -0.17586800 C -1.40850700 0.85447300 -0.10705400 C -0.76647000 -0.39566900 0.07779000 C -1.56428800 -1.54642100 0.20147000 H -3.54332000 -2.37129400 0.25325500 H -4.65892500 -0.17327900 -0.09901500 H -3.28240200 1.87732500 -0.32955200 H -1.09231000 -2.50844700 0.37528100 C -0.59992900 2.06463300 -0.26687800 H -1.10435600 2.97020300 -0.59485500 0 2 C 0.71195800 2.06859400 -0.00843100 C -2.82408900 -1.28496500 -0.75792200 H 1.30278500 2.97573800 -0.11056100 C -1.42889600 -1.32101300 -0.69689200 C -0.72934200 -0.43414200 0.11661800 phen_Vrad_a_2:

102 E = -501.7156579 H -0.46786300 -1.90309900 -1.17910400 H 1.67040000 -3.01078700 -0.66314100 C -2.39183000 -0.28439900 -0.50406000 H -3.30842000 0.30574900 -0.42810200 H -2.40798400 -0.76024900 -1.49540200 C -2.39183400 -1.38123700 0.56187400 H -3.35158000 -1.59618100 1.03930600 C -1.30916400 -2.04462700 0.90918000 H -1.09721900 -2.84109900 1.61133200

phen_rad_2: E = -501.7613673

0 2 C 1.22844500 2.05919500 0.30762200 C -1.03773500 0.54896300 -0.44107900 C -1.11796600 1.90690700 -0.23738100 C 0.01338300 2.66988800 0.14141000 H 2.10546100 2.63349500 0.59414100 H -2.07418600 2.40670300 -0.36987700 H -0.08987700 3.73955800 0.29481600 C 1.36253300 0.65922200 0.10569600 C 2.61636600 0.01056500 0.26838900 C 0.22237300 -0.10925900 -0.26780200 C 2.74212300 -1.34130400 0.07216000 0 2 H 3.47759900 0.60971700 0.55263100 C -0.57227800 2.40892900 -0.09970700 C 0.38609800 -1.50936300 -0.45960500 C 1.34831000 0.38488200 0.12129800 C 1.61076900 -2.10885600 -0.29621900 C 1.73604500 1.71942400 -0.02246600 H 3.70526800 -1.82533600 0.20018700 C 0.77672900 2.72958000 -0.11673200 H -0.47454600 -2.11481700 -0.72429300 H -1.32386100 3.18712700 -0.20246800 H 1.71340300 -3.17918100 -0.44616700 H 2.79365100 1.96737100 -0.06379200 C -2.27094100 -0.22506500 -0.84185900 H 1.08864100 3.76413600 -0.22148700 H -3.04110900 0.48048700 -1.17460900 C -0.98845700 1.07000900 0.02932200 H -2.05759600 -0.86268300 -1.71055300 C -2.37730700 0.70730200 -0.03970500 C -2.86168500 -1.08632200 0.25560200 C -0.00760200 0.06075100 0.16675800 H -3.77803800 -1.62442400 -0.01114200 C -2.76279000 -0.64408800 -0.08641100 C -2.36934700 -1.22321200 1.46577300 H -3.11854400 1.49328500 -0.14110400 H -2.63287200 -1.77167000 2.35862600 C -0.41372500 -1.38259900 0.39043400 C -1.84988700 -1.65469800 0.05457700 phen_rad_QST3_VrAtt_2: H -3.80805900 -0.88742300 -0.25477200 E = -501.6999106 H -0.31332900 -1.56811500 1.48158700 H -2.16412600 -2.69360100 0.00155900 C 2.37786900 -0.72072300 0.21494100 H 3.29731200 -0.41484000 -0.29376500 H 2.65060500 -0.87539400 1.27081400 C 1.85921700 -2.01956100 -0.35026000 H 2.56779600 -2.70472200 -0.80754000 C 0.56527000 -2.32655800 -0.27785200 H 0.18155200 -3.26371300 -0.67422500

Scheme 5

nap_Vrad: 0 2 E = -969.4946967 C 1.04921100 2.19150700 0.28224800 C -1.19201900 0.61713600 -0.36333000 C -1.32083000 1.97197700 -0.13692000 C -0.19243000 2.76817100 0.16161100 H 1.91299200 2.78921900 0.56067100 H -2.30753000 2.42747100 -0.15871800 H -0.31890200 3.83303000 0.33075400 C 1.22004100 0.79981300 0.06476100 C 2.47964400 0.15928900 0.24463600 C 0.09714700 0.02209100 -0.32049000 C 2.61735300 -1.19463800 0.03281500 H 3.33178000 0.75964000 0.55126800 C 0.26753000 -1.38437100 -0.57202500 C 1.52706600 -1.96343300 -0.41699200 0 2 H 3.58503200 -1.66736300 0.17128600 C 5.05048000 -0.47260700 -0.27513600 103 C 4.66006800 -1.50585400 0.55445300 C 4.07380300 -1.61349900 -1.38933500 C 3.31113700 -1.97301600 0.55719600 C 1.79752900 -1.76676500 0.26732000 C 2.35293600 -1.36573600 -0.31694700 C 2.62280100 -0.60679100 0.32072700 C 2.78871700 -0.29997900 -1.16642300 C 3.73457700 -0.49964500 -0.56381800 C 4.10080400 0.13576100 -1.14474900 C 4.46624200 0.73007700 -0.62245100 C 2.90310900 -3.02980700 1.42690200 H 5.31459400 0.80432300 -1.29732300 C 0.99660000 -1.83850200 -0.29205500 C 4.09544100 1.80913900 0.16991700 C 0.63529600 -2.85711400 0.57224200 C 3.02435000 1.69612200 1.08868000 C 1.59302900 -3.46257900 1.43414500 C 2.27057200 0.50954000 1.17281300 H 3.64108000 -3.48083700 2.08469200 H 4.93634300 -1.53670800 -2.04594600 H 6.07631900 -0.11943600 -0.26779000 H 4.65548800 2.73762700 0.11719000 H 5.37484000 -1.97724300 1.22371200 H 2.79333800 2.52434100 1.75081900 H 2.08362100 0.19017900 -1.82988200 H 1.70106500 0.30050700 2.07289600 H 4.40994300 0.95189400 -1.78907400 C 0.45210200 -1.72775400 0.94987300 C -0.06303700 -1.16778200 -1.15393600 H -0.09401000 -2.65633800 0.71688100 H 0.32794100 -0.96032000 -2.16065700 C -0.60808800 -1.71526100 3.12793400 C -1.12201500 -3.11452200 -2.19119000 H -1.20523900 -2.59134600 2.83136000 H -0.30788900 -3.78148900 -1.88335100 H -0.34358800 -1.79633900 4.18251200 H -2.07077100 -3.65149600 -2.15850800 H -1.20015900 -0.80532600 2.96118100 H -0.93584400 -2.75689600 -3.21173400 O 0.63637500 -1.67194800 2.39311000 O -1.25052400 -1.99563700 -1.28107100 C -0.35380700 -0.51003500 0.42752600 C -0.56988000 0.11935300 -0.49531300 C 0.17015000 0.70977300 0.45729700 C 0.08481100 1.24643400 -0.41691000 C -0.19913500 2.07891100 0.20173100 C 0.57022200 2.53226400 -0.18180700 C -1.24987400 2.69278400 0.92782000 C 1.40914900 2.80097700 0.94774600 C 0.51142600 2.84353100 -0.75404500 C 0.27359400 3.61255500 -1.07410200 C -1.59998600 4.02481800 0.67714700 C 1.90693500 4.08357000 1.16864500 H -1.77734800 2.11595900 1.68367600 H 1.65462300 1.98447600 1.61972300 C 0.15026000 4.17137300 -1.00473800 C 0.78083300 4.88836300 -0.83424000 H 1.33341600 2.37952600 -1.29189600 H -0.35785500 3.42040000 -1.93618100 C -0.90622600 4.76764400 -0.29376300 C 1.59942300 5.13844400 0.28531700 H -2.41062300 4.48405500 1.23411200 H 2.54056900 4.27016300 2.03009000 H 0.69209800 4.74417800 -1.75033900 H 0.54082500 5.69725900 -1.51722800 H -1.17988000 5.79947900 -0.48845600 H 1.99176300 6.13377300 0.46441400 Sn -2.26253600 -0.83121900 -0.50069100 Sn -2.57060400 -0.05482600 0.31894200 C -2.14675100 -2.76168400 -1.40275600 C -4.00572800 -0.13747100 -1.24875800 H -2.95240600 -2.90166100 -2.13230900 H -3.91062200 -1.09348200 -1.77314100 H -1.18917700 -2.87903000 -1.92359300 H -5.02525600 -0.04297200 -0.85787300 H -2.22986100 -3.55355900 -0.64917200 H -3.83609500 0.67198200 -1.96722100 C -3.78793700 -0.82867400 0.99197400 C -2.76112200 -1.70947500 1.64356900 H -4.77598400 -0.96133700 0.53656000 H -2.82759200 -2.63365800 1.05979200 H -3.63068900 -1.64166300 1.70995400 H -1.89174900 -1.77488500 2.30704000 H -3.78820700 0.12039200 1.54018300 H -3.66188200 -1.61243500 2.26067500 C -2.59124900 0.69673300 -1.93777000 C -2.78247400 1.77507800 1.39375900 H -3.46853000 0.47144300 -2.55502200 H -3.76038100 1.84156600 1.88492300 H -2.74713500 1.66340600 -1.44655000 H -2.00393300 1.86198600 2.16091300 H -1.71842700 0.79000900 -2.59349100 H -2.67858900 2.63142700 0.71660500 H 1.50413100 -3.70730500 -0.59811200 H 1.28140100 -4.26186300 2.09834900 H 3.56983400 -3.61042900 -1.99601900 H -0.39739600 -3.19182300 0.58874000 nap_rad_R: nap_rad_R_TS_Vratt: E = -969.5144225 E = -969.4692633

0 2 C -4.62010300 -1.47861000 1.06174400 0 2 C -3.33542600 -1.93987700 0.72676100 C 3.30643400 -2.76518600 -1.36886800 C -4.93873500 -0.13145700 0.88586600 C 2.14182100 -2.82809500 -0.55645600 C -2.38611900 -1.05646100 0.18892500 104 C -2.70201800 0.29508300 -0.00359500 C 2.42529500 -1.81911600 3.64603700 C -3.98427100 0.77955700 0.36800000 C 1.14924200 -2.03234800 3.02480700 C -4.27395700 2.19069500 0.27906700 C 0.40191700 -0.79000000 -1.06213400 H -5.26469800 2.54350900 0.54897100 C -0.77635800 0.01610300 -0.51860800 C -3.24783000 3.10476100 -0.04984000 C -0.73729100 1.27862900 -0.17507200 C -1.98354400 2.68056900 -0.40799700 C -1.13136000 2.53097500 0.31149600 C -1.65611700 1.21995100 -0.60894600 C -1.64343900 3.53971100 -0.56207000 H -5.92040100 0.24013600 1.16670600 C -2.02415300 4.78353200 -0.05996600 H -3.45376900 4.16973000 0.00006000 C -1.90343100 5.07092900 1.31383600 H -1.20794600 3.40875000 -0.62165400 C -1.39151400 4.08948400 2.18575400 H -1.67854800 1.03253300 -1.70342900 C -1.00673100 2.83947500 1.70230800 C -1.00641000 -1.53956100 -0.19520000 H 0.49601500 -0.58352000 -2.13421800 H -0.78957300 -2.47398200 0.34908800 H -1.73429900 3.31943300 -1.62110100 C -1.74895500 -2.95360400 -2.04689900 H -1.29441100 4.30658500 3.24481300 H -2.81501700 -2.71341500 -1.95378900 H -0.60452600 2.08411000 2.37060500 H -1.50509500 -3.14762400 -3.09209900 H -2.41829000 5.53586700 -0.73591600 H -1.52785000 -3.84807800 -1.44505800 H -2.20101800 6.04109400 1.69708000 O -0.91914400 -1.84073500 -1.63334800 C 4.22875500 -0.06857500 0.89940900 C 0.07383700 -0.49719100 0.03786400 C 2.74816800 0.19951900 -1.04939300 C -0.23279900 0.80185400 -0.18548900 C 4.02330300 0.41085400 -0.40006100 C 0.82985900 1.84832400 -0.12640200 C 3.21202700 -0.73235000 1.60070600 C 1.18703700 2.57909200 -1.27700300 H 4.39544100 -1.01080800 3.40361900 C 1.53282300 2.07705900 1.07049300 H 5.19213700 0.08974100 1.37955700 C 2.24200800 3.49963800 -1.23670600 O -0.03291200 -2.18198200 -0.95279300 H 0.65769200 2.39871500 -2.20929500 C 0.87999500 -3.14820000 -1.52323100 C 2.58907500 3.00066200 1.11377800 H 0.37938300 -4.11572100 -1.46916800 H 1.24073200 1.53367000 1.96507800 H 1.09912200 -2.90066400 -2.57096700 C 2.94992400 3.71084100 -0.04089700 H 1.81647800 -3.18313000 -0.95450700 H 2.51901100 4.04352200 -2.13403300 H -0.04751000 -1.80434000 1.27775900 H 3.12336100 3.16571500 2.04406300 Sn -2.62965000 -1.09821400 -0.39616200 H 3.76919000 4.42168900 -0.01102100 C -2.58819600 -2.55066100 1.16165400 Sn 2.06660800 -1.24323200 0.24459100 H -1.85121700 -3.32514900 0.92405400 C 2.81690900 -1.01468100 2.23160500 H -2.32171100 -2.08908700 2.11976600 H 2.00816500 -1.09486200 2.96697200 H -3.57271000 -3.02028300 1.27238300 H 3.56025000 -1.78968300 2.45219000 C -3.08224400 -1.99088600 -2.27389500 H 3.29509900 -0.03521700 2.34635200 H -2.95683400 -1.26725900 -3.08703000 C 1.88750000 -3.32372000 -0.19118300 H -2.40117100 -2.83040200 -2.44595400 H 1.45421900 -3.87023200 0.65502200 H -4.11437100 -2.35846200 -2.29775000 H 1.23887800 -3.45525200 -1.06558000 C -4.06520300 0.40487000 0.07855400 H 2.86595900 -3.76426500 -0.41384500 H -3.77290400 0.94322600 0.98819500 C 3.35972800 -0.26549700 -1.13093500 H -4.13812300 1.13993800 -0.73174300 H 4.30848300 -0.80528400 -1.23019300 H -5.05821000 -0.03129600 0.23950200 H 2.88606200 -0.20523500 -2.11695400 H 0.36077300 -2.52761800 3.58306600 H 3.57049300 0.75554300 -0.78949900 H 2.58996500 -2.15711600 4.66384900 H -3.07047500 -2.98277000 0.88308000 C 2.58355300 0.76582700 -2.36870500 H -5.35596200 -2.16468300 1.46805300 H 1.63122700 0.68858300 -2.87886200 C 5.06990400 1.11662600 -1.09056400 9anth_Vrad_dn_freq: H 6.02002500 1.25091300 -0.58086200 E = -1123.048143 C 3.60276800 1.44372700 -2.99363000 H 3.44508200 1.86576800 -3.98093300 C 4.87484800 1.61617100 -2.35287700 H 5.66676200 2.15045600 -2.86685500

9anth_radIM_RR_6_TS_VRatt_QST3_3: E = -1123.027556

0 2 C 1.72966400 -0.51635200 -0.36968600 C 1.93750900 -0.95698200 0.96314700 C 0.91543500 -1.62177900 1.73384800 0 2 C 3.42431900 -1.18656600 2.94868000 C 1.87274800 0.25250500 0.60445100 105 C 1.60968300 1.63587100 0.55005000 C 0.46708600 2.21394500 1.23951400 C 2.04716400 3.87081000 -0.44830100 C 0.92652700 4.38018400 0.17829600 C 0.15253300 3.56313400 1.05055500 C 0.81010800 -0.64282000 1.22041200 C -0.53931800 -0.44440200 0.50573700 C -1.07784600 0.75427100 0.36319100 C -2.27849800 1.42748300 -0.04291600 C -3.50734000 1.16056500 0.61338200 C -4.67612000 1.82216600 0.22034600 C -4.63999000 2.76345600 -0.82310500 C -3.42128800 3.04877800 -1.46460000 C -2.24675200 2.39779400 -1.07368200 H 1.10659200 -1.69347000 1.12507000

H -3.52339500 0.44020400 1.42717400 0 2 H -3.38959100 3.78030400 -2.26561100 C 3.54462400 -1.86001100 -0.24248200 H -1.29970500 2.61964500 -1.55719300 C 3.23644100 -0.46647500 -0.17667400 H -5.61314700 1.60642500 0.72370500 C 1.97996300 0.04919600 0.30078700 H -5.54788000 3.27391900 -1.12732200 C 3.97180900 1.85832500 -0.54419700 C 3.53450400 1.95001000 -0.93450900 C 2.74859200 2.34936600 -0.08440000 C 3.01408700 -0.29072500 -0.04929200 C 1.74802300 1.41078100 0.35520300 C 3.86487800 0.58891100 -0.81687200 C 0.85453900 -0.85580800 0.77520900 C 2.42010500 2.49167900 -0.27901900 C -0.50997600 -0.35358300 0.32265800 H 2.66522200 4.50086800 -1.08207700 C -0.73218900 0.97771200 0.40295000 H 4.14980700 2.59278800 -1.56074900 C -2.07299700 1.56045700 0.10453200 O 0.58233300 -0.39049700 2.64164900 C -2.26733900 2.41689500 -0.99681900 C 1.76663200 -0.60721000 3.44889300 C -3.54811200 2.89029500 -1.31073600 H 1.46288200 -0.46370900 4.48615300 C -4.65137900 2.52499400 -0.51930600 H 2.14922300 -1.62917700 3.31447300 C -4.46329700 1.68996100 0.59161800 H 2.55718300 0.10769300 3.18840700 C -3.18015200 1.21196300 0.90130800 H 0.05696300 1.68391400 2.09214800 H 1.01686400 -1.88369800 0.42846100 Sn -1.56619600 -2.14514500 -0.31189000 H -1.41560400 2.69111900 -1.61316300 C -0.05504200 -3.60622000 -0.67925200 H -5.30844700 1.41199700 1.21342100 H 0.31253800 -4.02900700 0.26361200 H -3.02614800 0.57300600 1.76731500 H -0.44697500 -4.42882300 -1.28826100 H -3.68880100 3.53580300 -2.17174400 H 0.79159200 -3.15850600 -1.21326300 H -5.64283800 2.89103000 -0.76542400 C -2.54355400 -1.52603300 -2.09273000 C 5.50224500 -0.01751600 -1.06736800 H -3.04548800 -2.36804700 -2.58240700 C 4.77340400 -2.30197700 -0.70263000 H -3.29320400 -0.75942900 -1.86416500 C 5.76650200 -1.37136600 -1.12178900 H -1.82116100 -1.09513100 -2.79442900 C 4.24264300 0.46711400 -0.59651800 C -2.97134300 -2.88574000 1.10905100 H 4.73441900 2.55607500 -0.88382400 H -3.22534900 -3.93134500 0.90088400 H 6.25024700 0.70437300 -1.38427100 H -2.55590300 -2.82256600 2.12060200 O 0.78179200 -0.88844600 2.24454600 H -3.89332900 -2.29447000 1.07677000 C 1.94875000 -1.47281100 2.87422900 H -0.68040800 3.99828500 1.59333500 H 1.74961300 -1.47495300 3.94644600 H 0.65156000 5.42120200 0.04060500 H 2.10365600 -2.50470100 2.52792100 C 3.38455600 -1.68171400 0.01064000 H 2.85246100 -0.88645400 2.66635100 H 2.78847600 -2.37892600 0.58833700 C 0.40788800 1.89917100 0.88715900 C 5.02221000 0.05681900 -1.48082900 H 0.42621600 1.71418400 1.97983800 H 5.64475300 0.73865900 -2.05401900 C 2.45540800 3.75980100 -0.08382500 C 4.50430100 -2.15727000 -0.63552800 H 3.22500500 4.45338900 -0.40933600 H 4.76300100 -3.20888200 -0.56530700 C 1.17419500 4.23196800 0.28233200 C 5.33857200 -1.27786900 -1.39788300 H 0.96992400 5.29697100 0.22807200 H 6.21526100 -1.67143700 -1.90114600 C 0.17588600 3.37545000 0.70047600 H -0.79823700 3.76487900 0.98079600 9anth_radIM_RR_6_freq_2: H 4.98444000 -3.36550800 -0.74502700 E = -1123.077783 H 6.72447900 -1.73180800 -1.48142100 Sn -1.95796700 -1.78413100 -0.32112000 C -3.28031200 -2.32081700 1.26475600 H -2.77854900 -2.19169400 2.23046900 H -4.17679100 -1.69057200 1.24847400 H -3.59230400 -3.36750200 1.17345500 C -0.80989100 -3.50408600 -0.85591500 H 0.00692500 -3.23866900 -1.53809000 H -0.37820300 -3.97330800 0.03669800 H -1.44021200 -4.24832600 -1.35612100 C -3.05159300 -1.04823300 -1.99025500 H -3.69600400 -0.21619200 -1.68106000 H -2.37040800 -0.68063200 -2.76572800 H -3.67984600 -1.83498600 -2.42367400 106 H 2.81007700 -2.59430300 0.06895300 H 3.07949000 3.49534300 -0.59173800 H 4.53234600 2.93974100 0.28132400 1anth_Vrad_dn_freq: C 3.73212600 -0.37557700 1.44693600 E = -1123.054101 H 3.11526800 -1.19089000 1.84394800 H 4.38047400 -0.79673600 0.66961400 H 4.36633400 0.00315100 2.25701500

1anth_radIM_RR_6_TS_Vratt_QST3_3: E = -1123.036438

0 2 C -0.88889200 0.55589400 -2.12302300 C -1.93467000 0.36998800 -1.13698400 C -1.76350900 0.67617400 0.22541200 C -4.23880000 -0.35045000 -0.64103400 C -4.06318200 -0.05203600 0.71954500 C -2.79626700 0.47646800 1.15872400 C 0.49197300 1.04047000 -1.72783400 0 2 C 1.24942800 0.11291700 -0.77987900 C 0.00132000 -2.50654400 0.15076000 C 1.17125800 -1.19247700 -0.76089400 C 1.32922200 -1.96732800 0.09528200 C 1.30067900 -2.52780000 -0.36715800 C 1.69217800 -0.83255200 0.87278200 C 2.31511300 -3.38062800 -0.90249600 C 3.50293500 -1.86288100 -1.05372700 C 2.40973800 -4.70957300 -0.49087500 C 3.84245200 -0.69268100 -0.34253000 C 1.50436400 -5.23730300 0.45144800 C 2.94101900 -0.18760900 0.65787200 C 0.49310100 -4.41088400 0.98061100 C -1.07775900 -1.72070100 0.86719800 C 0.38263800 -3.07963100 0.58310300 C -1.18641300 -0.29829100 0.28432000 H 1.08482100 1.17147900 -2.64798500 C -0.13108500 0.48493200 0.17161100 H 3.01346700 -2.97473600 -1.62764100 C 0.39867000 1.78419400 -0.07763000 H -0.20928500 -4.81298200 1.70396100 C 0.14473700 2.84608100 0.83148600 H -0.40198900 -2.44236900 0.98074500 C 0.73558500 4.09914400 0.63788000 H 3.19040400 -5.34293400 -0.90035300 C 1.59445100 4.31874800 -0.45356900 H 1.58392600 -6.27258600 0.76538500 C 1.86036300 3.26991000 -1.35327100 C -3.40506500 -0.46099600 -2.96680100 C 1.27861300 2.01352900 -1.16757200 C -1.12988100 0.24909500 -3.44240700 H -2.03332900 -2.25469700 0.73749600 C -2.39667900 -0.26648000 -3.87582000 H -0.50718700 2.66491800 1.68202100 C -3.20925500 -0.15098400 -1.57552500 H 2.53325100 3.43075400 -2.18921000 H -5.19333400 -0.74555000 -0.98259400 H 1.49961600 1.19437200 -1.84598400 H -4.36857300 -0.85343100 -3.28022100 H 0.53053400 4.90426600 1.33644700 O 0.47533000 2.32078600 -1.02103800 H 2.05522100 5.29056300 -0.59751100 C -0.12329200 3.41166900 -1.75902600 C 1.88867300 -3.67359400 -1.60365700 H 0.02989800 4.31089800 -1.16108600 C -0.32867900 -3.61759600 -0.60327200 H 0.36281800 3.52890000 -2.73727800 C 0.63581400 -4.23046400 -1.46221000 H -1.19617100 3.24083700 -1.90536400 C 2.26318100 -2.50580700 -0.85660600 H -0.81751200 1.08427400 0.56755200 H 4.20549800 -2.27162600 -1.77688100 C -2.62367500 0.78937100 2.55230700 H 2.60796900 -4.09997800 -2.29774800 H -1.66992700 1.19640900 2.87732100 O -0.84707900 -1.56169400 2.29934100 C -5.10645300 -0.25336300 1.68910500 C -0.75827100 -2.82449600 3.00544700 H -6.05910600 -0.65278800 1.35172500 H -0.70797800 -2.58002500 4.06687400 C -4.90420800 0.05352800 3.01341200 H -1.64578900 -3.44345300 2.81009300 H -5.69543700 -0.10090100 3.73978700 H 0.13814300 -3.38125400 2.70631800 C -3.64229700 0.58458500 3.45215900 H 1.12404600 -0.59859200 1.76782200 H -3.50312400 0.82335200 4.50133600 Sn -3.09550100 0.48370400 -0.31350500 H -0.34062500 0.39001700 -4.17651700 C -4.29477900 -1.18796000 -0.87858000 H -2.54519300 -0.50140200 -4.92427500 H -4.58925900 -1.76953700 0.00257700 Sn 2.49889200 1.16451600 0.63895600 H -5.20729100 -0.85747900 -1.38755700 C 1.32553000 2.00916200 2.20193400 H -3.74231600 -1.84497700 -1.56033200 H 0.59578600 2.70787400 1.77926300 C -2.75989000 1.82434200 -1.92580900 H 0.79588700 1.21747700 2.74518700 H -3.69054000 2.31338400 -2.23451900 H 1.95841400 2.54777700 2.91678000 H -2.04414700 2.59853600 -1.62516700 C 3.69385100 2.62252000 -0.34894900 H -2.34257200 1.29385700 -2.78847900 H 4.10168200 2.21572300 -1.28134500 C -3.97256900 1.49698700 1.34172800 107 H -3.46136300 2.45075600 1.51373200 H 5.87911600 2.87554700 0.40073700 H -5.03367000 1.70280000 1.16104000 C 3.91504300 2.55858300 1.26176500 H -3.88376200 0.89082400 2.24967800 H 3.92234700 3.47808900 1.83703600 C 5.07654300 0.00394100 -0.57037200 H -0.29003400 -4.40714200 -0.76885000 C 3.30818000 0.97658000 1.40063600 H 1.77058100 -5.07167700 -2.02271700 C 4.49934500 1.62931600 1.15416300 Sn -2.88334000 0.06084900 -0.24944400 H 4.76049100 2.52206300 1.71241600 C -3.92475600 1.01470800 1.35017300 C 5.39370000 1.13492600 0.15193200 H -3.55774800 0.65000800 2.31611600 H 6.32743200 1.65641100 -0.03313000 H -3.77975900 2.10009800 1.30719200 H 5.75774200 -0.37727000 -1.32658800 H -4.99906900 0.80668500 1.28827100 H 2.61705000 1.35248800 2.15092600 C -3.91762100 -1.73986400 -0.74844700 H -1.34199200 -4.01077200 -0.56879700 H -3.34794800 -2.33576500 -1.47165300 H 0.36068800 -5.11272300 -2.03078500 H -4.09295100 -2.35224000 0.14420800 H -4.89175600 -1.50825700 -1.19478300 1anth_radIM_RRdn_6_freq: C -2.77239300 1.34534400 -1.94158800 E = -1123.090832 H -2.37596700 2.32585000 -1.65077500 H -2.10402900 0.92088200 -2.69903600 H -3.76270700 1.48616000 -2.39012500

9panth_Vrad_dn_freq_S: E = -1123.063552

0 2 C 0.55224900 -2.54166400 -0.08120800 C 1.66697400 -1.69395000 -0.08121800 C 1.54335900 -0.38755800 0.68125900 C 3.92006400 -1.11406300 -0.89232800

C 3.88921100 0.14291000 -0.20383500 0 2 C 2.75737800 0.51641200 0.57872000 C 1.18969400 -0.57712400 0.92960600 C -0.68288900 -2.04476200 0.64909600 C 1.93885900 0.66127800 1.07179200 C -0.92414000 -0.57344200 0.32143700 C 1.41616200 1.76196100 1.80530800 C 0.16070900 0.23948800 0.34037300 C 3.92679900 2.00819500 0.60056900 C 0.04182900 1.69460300 0.04225100 C 3.39644400 3.07016200 1.32040500 C 0.69472200 2.25422500 -1.07259600 C 2.12653500 2.94667700 1.92934800 C 0.52125000 3.60650600 -1.39136100 C -0.21111900 -0.68386800 1.51172800 C -0.29618300 4.42310100 -0.58987800 C -1.23651300 -0.03912500 0.56982000 C -0.93268100 3.87837900 0.53524400 C -1.31278900 1.23081100 0.27774000 C -0.76309400 2.52051200 0.84846100 C -1.47761800 2.52483200 -0.20868900 H -1.54553800 -2.67067200 0.37289800 C -0.68839300 2.97509900 -1.31809800 H 1.32767100 1.62331500 -1.69097700 C -0.82770400 4.27264800 -1.80456300 H -1.55498600 4.50521100 1.16638800 C -1.74302300 5.16871200 -1.21496300 H -1.23916600 2.09655100 1.72920100 C -2.52134700 4.74317900 -0.11945500 H 1.01961400 4.02429600 -2.25996600 C -2.39763300 3.44883600 0.38355600 H -0.42797400 5.47156800 -0.83691700 H -0.25789300 -0.22740800 2.51068000 C 2.84385900 -3.27584200 -1.51812200 H 0.02524500 2.28708800 -1.76121800 C 0.58221400 -3.75825900 -0.77480300 H -3.22774600 5.42960900 0.33718900 C 1.74228900 -4.12894400 -1.48631900 H -2.99923600 3.12348700 1.22663200 C 2.82580800 -2.03454300 -0.82325300 H -0.22218400 4.59557600 -2.64561600 H 4.79858000 -1.37606100 -1.47710000 H -1.84655300 6.17728300 -1.60045400 H 3.72841200 -3.54586800 -2.08861200 C 3.76550000 -0.33196000 -0.31468400 O -0.51914900 -2.12317100 2.10441600 C 1.70587000 -1.60958800 0.19936900 C -0.34984900 -3.47661300 2.59177200 C 3.21961600 0.78596000 0.45440200 H -0.34153100 -3.41292500 3.68040600 H 4.90088000 2.12688600 0.14060600 H -1.18521600 -4.11393700 2.26644600 O -0.64231300 -2.06687200 1.61917900 H 0.59186700 -3.91342500 2.23721200 C -0.05287100 -2.81097300 2.71251000 H 1.43191200 -0.65962500 1.74482700 H -0.46673500 -3.81866500 2.65910900 C 2.80406200 1.70712400 1.31723000 H -0.31894000 -2.35318900 3.67374600 H 1.95480700 1.97742200 1.93856800 H 1.03843800 -2.85256600 2.61695500 C 5.00578700 1.02245100 -0.26194600 H 0.43839000 1.68891000 2.26833300 H 5.86209200 0.73893500 -0.86838100 H 1.12864900 -2.52379500 0.08298600 C 5.01839200 2.21681000 0.45365900 Sn -2.57328200 -1.47902800 -0.34499200

108 C -1.48590600 -2.99493600 -1.36996200 H 1.00668400 -2.80059300 3.32433000 H -1.10417800 -3.71689100 -0.64030800 H 1.93983900 -1.28295900 3.47200400 H -0.63593500 -2.55520100 -1.90434600 H 0.28222300 1.12428600 2.35662000 H -2.11932800 -3.51739900 -2.09577800 Sn -2.37248800 -1.62919600 -0.52771300 C -3.92019600 -2.28678100 1.08999100 C -1.55078700 -3.57639000 -0.82592200 H -4.42957200 -1.48209600 1.63161600 H -1.47044400 -4.11779700 0.12379600 H -3.36274400 -2.89394700 1.81020500 H -2.18422200 -4.16522700 -1.49915900 H -4.68101300 -2.91215600 0.60907700 H -0.55178000 -3.50674900 -1.27259400 C -3.64485800 -0.28000100 -1.74587000 C -2.73292300 -0.63977300 -2.37366000 H -2.95455300 0.16203700 -2.47415900 H -3.40254600 -1.22678900 -3.01241500 H -4.16060500 0.54166500 -1.23469900 H -3.19156900 0.33969400 -2.19509000 H -4.39135700 -0.86950900 -2.29083600 H -1.79060300 -0.48080300 -2.90910500 H 1.70486200 3.77810900 2.48371500 C -4.16332200 -1.75130700 0.62121800 H 3.95405800 3.99626400 1.41235100 H -4.77762800 -0.85882600 0.45602800 C 2.99671500 -1.52183500 -0.43484400 H -4.75147800 -2.63153800 0.33792000 C 3.49928900 -2.61727200 -1.18507100 H -3.92798800 -1.81927000 1.68880600 C 4.73855400 -2.54622600 -1.80367000 H 2.27912200 -2.64793900 0.17868300 H 2.89236700 -3.51505600 -1.26701500 C 5.09520600 0.79343000 -1.05895700 C 5.51091800 -1.36492900 -1.68457300 C 4.61471800 -1.96554700 -0.97887600 H 5.11681300 -3.38640500 -2.37633300 C 5.99668200 -0.08943600 -1.63978800 H 6.48129600 -1.30413800 -2.16629000 C 5.75630600 -1.48524200 -1.60201200 C 5.03158200 -0.28361800 -0.95590300 H 4.41557900 -3.03324100 -0.94347300 H 5.64479300 0.60722600 -0.88478500 H 6.46400600 -2.17001200 -2.05727400 H 6.89152100 0.29033600 -2.12174900 9panth_radIM_RR_6_TS_Vratt_QST3: H 5.30829200 1.85557000 -1.09490800 E = -1123.039181 H 2.24861000 4.55544800 0.67379100 H 0.37468300 3.59660500 2.00209800

9panth_radIM_RRdn_6_freq: E = -1123.0793896

0 2 C 1.59241400 -0.74147700 0.85410200 C 1.84401600 0.67871700 0.90548700 C 0.88877300 1.54143500 1.55815000 C 3.07300200 2.64465200 0.13504200 C 2.13282600 3.47820900 0.74339900 C 1.06465700 2.94031900 1.48198200 C 0.23668200 -1.25340100 1.30284500 C -0.87453300 -0.52016100 0.53826800 0 2 C -0.89590900 0.80629000 0.48425500 C 1.76996600 -0.73222000 0.26083300 C -1.75071000 1.86867900 0.01562200 C 1.91156000 0.67346600 0.40969200 C -3.06936900 2.00386900 0.51573400 C 0.69573600 1.45664500 0.88609400 C -3.89495200 3.03906300 0.06039200 C 3.22752200 2.73244200 0.18731700 C -3.41817800 3.95793500 -0.89022000 C 2.07044900 3.51584400 0.43313500 C -2.10309900 3.84212900 -1.37518300 C 0.85226600 2.94507200 0.71269200 C -1.26993200 2.81446000 -0.92061100 C 0.42263000 -1.35130700 0.55472700 H 0.19383800 -2.33506200 1.09705100 C -0.73354700 -0.46972000 0.11535400 H -3.42530800 1.29805700 1.26196700 C -0.60709500 0.86439100 0.30236100 H -1.72973100 4.55491800 -2.10345000 C -1.75881300 1.77789700 0.04447500 H -0.24999600 2.72298600 -1.28322100 C -2.29381500 1.90024500 -1.25082400 H -4.90570100 3.13131600 0.44480700 C -3.42587500 2.69755400 -1.48308400 H -4.06001300 4.75878400 -1.24249400 C -4.03300300 3.38402500 -0.42105500 C 3.91908300 0.32759400 -0.41398600 C -3.49747800 3.27541200 0.87417000 C 2.48307700 -1.58003800 0.23777600 C -2.36643500 2.48198400 1.10285900 C 3.68367600 -1.07696600 -0.37770000 H 0.37665800 -2.34767300 0.08519800 C 2.95149900 1.22818400 0.21015200 H -1.81393200 1.37365700 -2.07156800 H 3.90076000 3.09393800 -0.40120800 H -3.96711400 3.79870600 1.70086500 O -0.02097300 -1.06136200 2.72647300 H -1.96820800 2.37792300 2.10916200 C 0.94426000 -1.73176700 3.57480100 H -3.82868500 2.78349400 -2.48735000 H 0.58705000 -1.61519200 4.59825600 109 H -4.91046400 3.99731000 -0.59848900 C 0.91840800 1.51958200 0.23348900 C 4.27763200 0.48568100 -0.27198800 C -0.13578900 2.43272800 0.43579700 C 2.83670400 -1.51080600 -0.14376100 C -0.04242600 3.78403700 -0.00986400 C 3.14018300 1.30131800 0.12479300 C -1.09785500 4.67258800 0.19972100 H 4.16367300 3.23606200 -0.01794900 C -2.26737500 4.25206800 0.86138600 O 0.21915800 -1.53349100 2.00058800 C -2.36844400 2.92363000 1.31729200 C 1.12283100 -2.49470800 2.59924200 C -1.32249600 2.02231900 1.11674000 H 0.79306900 -2.62550400 3.63051400 H 1.60798200 0.34983900 -2.47385500 H 1.07023800 -3.45837300 2.07051200 H 0.86020300 4.10790000 -0.51849100 H 2.15812200 -2.13347400 2.58321700 H -3.26802100 2.59107100 1.82583100 H 0.61214600 1.25919400 1.97599400 H -1.40184900 0.99633100 1.46679000 H 2.71319500 -2.58550000 -0.26678600 H -1.01481600 5.69639200 -0.15136100 Sn -2.57565200 -1.45001100 -0.34242800 H -3.08376300 4.94852700 1.02119900 C -4.17195900 -0.57983200 0.76014900 C -3.60590400 -1.05627000 -0.05763700 H -3.87763500 -0.43602700 1.80554700 C -1.66472000 -2.09027800 1.08133400 H -4.42966200 0.40010100 0.33972100 C -2.68360400 -0.47561500 -1.03313500 H -5.06212100 -1.21887700 0.73204700 H -4.20412300 0.53823500 -2.21656500 C -2.23757200 -3.47455800 0.24035900 O 1.67415600 -1.50306600 -1.53430100 H -1.64341100 -4.01006300 -0.50954100 C 1.41590700 -2.32983300 -2.69350500 H -1.69874300 -3.49310700 1.19544600 H 1.95907000 -3.26226500 -2.53616700 H -3.18545100 -4.00947300 0.36770300 H 1.77747300 -1.83859500 -3.60737500 C -3.01813900 -1.37941100 -2.43040000 H 0.34382300 -2.53663800 -2.79361300 H -3.58319700 -0.47038700 -2.66634800 H 0.26276000 -1.73440400 0.24715000 H -2.09723000 -1.37948700 -3.02451700 H -1.29276800 -2.71694900 1.88763800 H -3.61966900 -2.24631600 -2.72743100 Sn 3.32785300 -0.33315600 0.59005500 H -0.01879700 3.57208800 0.87151400 C 2.81376100 -2.17549500 1.52303200 H 2.15158400 4.59743500 0.38045300 H 2.49447000 -2.89006900 0.75741900 C 4.11424300 -0.92734400 -0.40188500 H 1.99236100 -2.02888900 2.23441200 C 5.22174700 -1.73655600 -0.79061900 H 3.66743000 -2.59469400 2.06794300 C 6.45770500 -1.17234200 -1.04526400 C 4.85984800 -0.58311600 -0.86555200 H 5.07439000 -2.80921700 -0.88380100 H 5.10108100 0.37308300 -1.34307900 C 6.62671400 0.23335600 -0.91916300 H 4.51461200 -1.28212900 -1.63441000 H 7.29751400 -1.79287500 -1.33961600 H 5.77558000 -0.98014000 -0.41322200 H 7.59708900 0.67710700 -1.11648300 C 3.91945000 1.07432800 2.07635600 C 5.56273300 1.03785500 -0.54452100 H 3.04795300 1.37095700 2.67209900 H 5.72462400 2.10548100 -0.45544600 H 4.33413900 1.97713300 1.61424500 H 4.67342000 0.65344900 2.75134800 1panth_Vrad_dn_freq_S: H -0.17379400 1.17522700 -3.53789200 E = -1123.0634101 H -2.62476000 1.54358000 -3.79981300 C -3.08618900 -1.85742200 0.99741800 C -3.96575000 -2.42407000 1.95753900 C -5.33301600 -2.20541100 1.88600500 H -3.54617100 -3.03387400 2.75290000 C -5.85727600 -1.40666800 0.84018200 H -6.00012900 -2.63981600 2.62301400 H -6.92630000 -1.23085800 0.78054500 C -5.01073500 -0.84745500 -0.10824100 H -5.44340400 -0.23992200 -0.89433800

1panth_radIM_RR_6_TS_Vratt_QST3: E = -1123.039853

0 2 C -0.80129800 -1.54286900 0.17740800 C -1.28421100 -0.70743500 -0.90214800 C -0.37680600 -0.09043300 -1.81940100 C -3.14498400 0.34379000 -2.09815200 C -2.25742600 0.91652800 -2.99465200 C -0.86755900 0.69959400 -2.84949500 0 2 C 1.12681900 -0.15314300 -1.61931400 C 0.58433100 -2.25984000 0.13833500 C 1.58327500 0.53262900 -0.32105300 110 C 1.68006000 -1.38198800 0.36237700 C 1.52753300 -0.26912100 1.29458300 C 3.92695200 -0.51396000 -0.28090500 C 3.72460100 0.59789200 0.59160500 C 2.54553000 0.66909000 1.40622500 C -0.77979400 -1.90296600 0.70228700 C -1.19636800 -0.49031900 0.26426600 C -0.35648100 0.52953200 0.37561600 C -0.31219900 1.96360800 0.23974800 C -1.18850600 2.78859200 0.98698600 C -1.13091200 4.18152100 0.85528700 C -0.19457300 4.77238600 -0.01026300 C 0.69594600 3.96064500 -0.73532000 C 0.64793500 2.56867500 -0.60493500 H -1.50460500 -2.64465500 0.32974500 H -1.89806600 2.32592700 1.66849500 H 1.42766600 4.41332300 -1.39662900 H 1.33919100 1.93517200 -1.15372500 H -1.81056300 4.80581000 1.42656200

H -0.15278800 5.85201400 -0.11179900 0 2 C 2.99138400 -2.65362300 -1.25141700 C 1.30506000 0.11865000 0.82644300 C 0.72308700 -3.34070500 -0.72502000 C 1.83474900 -1.11317700 0.11142800 C 1.94491200 -3.55612400 -1.40105100 C 0.93310300 -2.17342700 -0.08502300 C 2.87617100 -1.53289500 -0.38737900 C 3.55294100 -2.39294500 -1.02006300 O -0.83984700 -1.91945600 2.16186600 C 2.65702400 -3.44662100 -1.21229200 C -0.51181200 -3.21090100 2.73218400 C 1.33748000 -3.33751800 -0.74479300 H -0.68305900 -3.12521300 3.80557600 C -0.48003300 -2.01102300 0.43675000 H -1.15902700 -3.99618900 2.31578500 C -1.01138600 -0.60734100 0.18962500 H 0.53606700 -3.47205600 2.54007200 C -0.15010100 0.41643700 0.39358200 H 0.79675900 -0.36941200 2.09115800 C -0.59883500 1.83610700 0.28357400 Sn -3.17795400 -0.13447100 -0.48391600 C -0.11396400 2.67636800 -0.73767100 C -3.92461600 -2.01953100 -1.14719200 C -1.57881600 4.46912200 0.01261300 H -4.08709700 -2.69441900 -0.29889500 C -2.05147900 3.64608500 1.04515100 H -4.88155900 -1.89194400 -1.66609700 C -1.56242400 2.33678000 1.17922100 H -3.22189100 -2.49519300 -1.84115300 H -1.12249200 -2.77695200 -0.02632800 C -3.04636800 1.26982000 -2.07312900 H 0.63008000 2.29475300 -1.43157800 H -4.02828900 1.44609500 -2.52668500 H -2.79511600 4.01925300 1.74228000 H -2.65989000 2.22436200 -1.69760100 H -1.91801600 1.69712100 1.98298000 H -2.36335800 0.90791800 -2.84906700 H -1.96012800 5.47904700 -0.09779000 C -4.40269900 0.62091700 1.08998400 C 4.09952500 -0.07487400 -0.17031700 H -5.44549300 0.30996600 0.96097200 C 2.24453100 1.28279700 0.76708700 H -4.04504200 0.24601400 2.05531800 C 3.16374000 -1.20875400 -0.35238600 H -4.36957200 1.71618600 1.10651200 H 4.55903600 -2.48996600 -1.41153900 H -0.11855500 -4.00733900 -0.89689100 O -0.53927600 -2.20014900 1.89269100 H 2.46378200 1.47627500 2.12895200 C -0.16022100 -3.53081400 2.32164000 C 5.13078100 -0.57310400 -1.02609900 H -0.37679600 -3.58265900 3.38922500 C 6.09683500 0.42358200 -0.92185000 H -0.74707100 -4.29405200 1.78935400 C 4.72368400 1.60588400 0.68581600 H 0.90673200 -3.71761600 2.14936800 C 5.89190500 1.52599900 -0.05753500 H 1.89938700 2.23448400 1.16208600 H 4.55187500 2.44414800 1.35540100 Sn -3.05083200 -0.35837400 -0.39428500 H 6.64715000 2.30109500 0.02129600 C -4.28948200 0.11243700 1.27742100 H 7.00918400 0.35627900 -1.50529700 H -3.85211900 -0.29357600 2.19643600 H 5.31370600 -1.40342900 -1.69892700 H -4.38812500 1.19868300 1.38511700 H 3.90189900 -2.81155000 -1.81798400 H -5.29052400 -0.31567500 1.15128300 H 2.05412600 -4.40841200 -2.06345000 C -3.65043200 -2.25596700 -1.16735600 H -2.96442200 -2.60351400 -1.94871200 1panth_radIM_RRup_6_freq_2: H -3.67972900 -3.00908400 -0.37080000 E = -1123.083974 H -4.65365300 -2.18738500 -1.60404200 C -3.21255500 1.14855200 -1.88724500 H -3.06896100 2.13953400 -1.43937100 H -2.44540800 1.01034600 -2.65728300 H -4.19751900 1.12004200 -2.36750000 H 2.98010000 -4.34285700 -1.73138800 H 0.62867500 -4.14780900 -0.89631500 C 3.59174500 1.16197900 0.35473200 C 4.47848700 2.27680200 0.47009800 C 5.45959600 -0.15494100 -0.51172600 C 5.81618100 2.17219800 0.11262300 H 4.08374700 3.21262300 0.85661900 C 6.31692700 0.94436800 -0.37450800 H 6.47757100 3.02656800 0.21274100 111 H 7.36366500 0.85159200 -0.64351500 H -1.76039500 -1.52034600 2.72307100 H 1.19261400 -0.16767000 1.89240900 H 0.47414000 -0.21537700 -3.75485000 H 5.87193300 -1.08524400 -0.88657600 H 1.49365100 -1.51274600 2.82251800 C -0.60482500 3.98137300 -0.87640700 C 3.35600500 0.05438200 -1.94641900 H -0.23685900 4.61401500 -1.67762500 C 4.75064600 0.42418100 -2.06753300 C 5.58869700 0.37870400 -0.99224900 1pyr_Vrad C 4.13050900 -0.86214100 2.82815400 E = -1199.262719 C 5.47426700 -0.49848700 2.67776400 C 5.96155800 -0.09071700 1.42847700 C 5.11057500 -0.04130800 0.30850300 H 2.85900600 0.41918000 -4.01338700 H 5.11281500 0.74271600 -3.04090400 H 6.63370600 0.65950500 -1.08939300 H 7.00411500 0.19262700 1.31519900 H 6.14152000 -0.53165900 3.53252400 H 3.75490500 -1.17835300 3.79713500

1pyr_radIM_RR_6_TS_Vratt_QST3_3: E = -1199.2399943

0 2 C 0.62384900 -0.66871800 -1.65833400 C 1.47974600 -0.72923900 -0.53003200 C 1.01298400 -1.14835600 0.77825500 C 3.73881200 -0.41067800 0.45381300 C 3.25067800 -0.82332900 1.72908800 C 1.85781100 -1.19177200 1.85010100 C -0.85949600 -0.97187500 -1.56176100 C -1.63844300 -0.00238300 -0.67036200 C -1.40996900 1.28051200 -0.57383600 0 2 C -1.33575900 2.63139800 -0.24406200 C 0.57997200 -2.03668500 0.46585500 C -0.46370800 3.06829000 0.80668000 C 1.54344700 -1.02725300 0.65952800 C -0.37386600 4.41950800 1.13323100 C 1.24416800 0.14758200 1.47515400 C -1.13386100 5.38108900 0.43639200 C 3.70930700 -0.00255400 0.01968300 C -1.99153500 4.96713700 -0.60273800 C 3.38112800 1.16955700 0.77401000 C -2.09671900 3.62079800 -0.94609300 C 2.15859800 1.19522200 1.52876300 H -1.28387700 -0.93998300 -2.57825400 C -0.84105200 -1.80581900 0.93845900 H 0.12932600 2.32615200 1.33318700 C -1.39356300 -0.49399100 0.35502000 H -2.57784900 5.70447400 -1.14217400 C -0.70077700 0.63246900 0.43216600 H -2.75647500 3.30340900 -1.74736200 C -0.83486700 2.04823500 0.20705800 H 0.29116900 4.73341100 1.93156900 C -1.83962400 2.78754400 0.87978000 H -1.05741600 6.43152200 0.69597200 C -1.96221700 4.16621400 0.67016200 C 1.13926500 -0.26080600 -2.89639300 C -1.08291200 4.82985300 -0.20233500 C 2.48310500 0.09899200 -3.04607300 C -0.06879900 4.10659600 -0.85576800 C 2.85379800 -0.36620100 -0.67632800 C 0.06485400 2.73002200 -0.64577800 O -1.15477100 -2.28644600 -0.99622900 H -1.45603000 -2.65846600 0.60800000 C -0.58236500 -3.40053700 -1.72038600 H -2.50551100 2.26892400 1.56501400 H -0.96561600 -4.30628500 -1.24904600 H 0.61781800 4.61779300 -1.52279400 H -0.88781400 -3.37357000 -2.77534000 H 0.85288700 2.16728200 -1.13825800 H 0.51203900 -3.38429300 -1.65878100 H -2.73948500 4.72246500 1.18445200 H -0.02337800 -1.44550700 0.88347500 H -1.18087200 5.89822500 -0.36531200 Sn -3.20368400 -0.93877700 0.49399800 C 0.89413100 -3.16383000 -0.31242900 C -4.48789600 -2.07011700 -0.77062200 C 2.14367100 -3.28834600 -0.92645200 H -3.95656500 -2.95973300 -1.12378100 C 2.78486300 -1.10119500 -0.03423500 H -5.39183200 -2.38399100 -0.23631300 O -0.97243500 -1.69800500 2.38899400 H -4.79214700 -1.47692500 -1.64021500 C -0.52488600 -2.88491600 3.09005300 C -4.24409900 0.72599700 1.32549300 H -0.75579500 -2.72522300 4.14359000 H -4.99603000 0.40482500 2.05566100 H -1.05622200 -3.77623200 2.72618500 H -3.53898900 1.39910300 1.82832000 H 0.55427500 -3.03465100 2.96221400 H -4.74848500 1.29935200 0.53884200 H 0.49347600 0.04945500 2.25336600 C -2.40073200 -2.12505000 2.06989000 Sn -3.32153600 -0.46098800 -0.59142300 H -3.20425100 -2.55217700 2.68117600 C -3.69208400 -2.45258700 -1.26019300 H -1.80603700 -2.94054100 1.64537000 H -3.88602900 -3.12008900 -0.41274300 112 H -4.56628200 -2.48035000 -1.92067700 C 3.01164200 -0.83854000 -0.09360900 H -2.83125700 -2.83940700 -1.81816300 O -0.77315300 -2.16233700 1.91807800 C -3.23727100 0.91385200 -2.20899000 C -0.32548700 -3.45936700 2.38248800 H -4.15748200 0.88287600 -2.80320900 H -0.62801800 -3.53273100 3.42772900 H -3.10225800 1.93298000 -1.82891400 H -0.80053000 -4.26589200 1.80427600 H -2.39080600 0.68151000 -2.86431900 H 0.76428500 -3.55763200 2.30449800 C -4.80301900 0.12912800 0.82239200 H 0.83843200 0.08775300 2.00019200 H -5.79188200 -0.24689100 0.53670800 Sn -3.25553700 -0.55788900 -0.45742000 H -4.55494700 -0.26115600 1.81533900 C -3.62192300 -2.51017300 -1.24139500 H -4.85515400 1.22221700 0.88185500 H -3.57331300 -3.26315200 -0.44528700 H 0.14316200 -3.93827100 -0.45067300 H -4.61924800 -2.56124000 -1.69349200 H 1.96260900 2.05179800 2.16791400 H -2.88741200 -2.77295000 -2.01198300 C 3.09374100 -2.25219400 -0.82036700 C -3.54342200 0.92116700 -1.95959600 C 4.36357300 -2.30693300 -1.51098600 H -4.53670100 0.82611800 -2.41359400 C 5.24696600 -1.26701700 -1.44679500 H -3.45033200 1.92480000 -1.52705700 C 4.29728400 2.24345800 0.79894500 H -2.78967300 0.81965000 -2.74842000 C 5.50892000 2.16735300 0.09962100 C -4.57530600 -0.23146200 1.18577900 C 5.83391000 1.02096000 -0.63765700 H -5.52205500 -0.76227600 1.03432900 C 4.94334300 -0.07230200 -0.68793900 H -4.11593700 -0.59841000 2.11063400 H 2.37980900 -4.16794400 -1.51853700 H -4.79206200 0.83667800 1.30009500 H 4.59496300 -3.19528600 -2.09219800 H 0.83626600 -4.03415400 -0.65130800 H 6.19611200 -1.31342300 -1.97362400 H 1.39101800 2.51176200 1.25522200 H 6.77403200 0.96590500 -1.17913300 C 3.59821400 -2.01261200 -0.64735500 H 6.20126700 3.00222800 0.13040500 C 4.99300500 -1.99176300 -1.01804800 H 4.05102100 3.13262500 1.37236900 C 5.74505300 -0.86023500 -0.86580600 C 3.99046800 2.74738400 0.60321000 1pyr_radIM_RR_6: C 5.34310200 2.72550000 0.23524300 E = -1199.284796 C 5.93291200 1.54888800 -0.23474600 C 5.16507200 0.35716400 -0.34694200 H 3.25118800 -4.05978900 -1.26081300 H 5.43133400 -2.89892000 -1.42465800 H 6.79454600 -0.85052300 -1.14726300 H 6.97908400 1.53442000 -0.52653200 H 5.93444000 3.63208400 0.31280800 H 3.53690600 3.66696100 0.96226600

Scheme 6

HSnMe3_freq: E = -123.6054157

0 2

C 0.87540900 -1.99747500 0.08330500 0 1 C 1.64566500 -0.85805100 0.29113100 Sn 0.00000000 0.00000000 0.23681500 C 0.98145600 0.34720200 0.93086600 C 0.00000000 2.01129800 -0.46752600 C 3.80344500 0.36138100 0.03621800 H 0.00000000 2.03191900 -1.56283200 C 3.19017000 1.57563200 0.51991800 H -0.88702200 2.54872900 -0.11517500 C 1.82848800 1.58653200 0.88956700 H 0.88702200 2.54872900 -0.11517500 C -0.58719500 -1.95660900 0.47425400 C -1.74183600 -1.00564900 -0.46752600 C -1.21869500 -0.60215500 0.18514600 H -1.75969300 -1.01596000 -1.56283200 C -0.46963300 0.50011000 0.41977600 H -1.76375400 -2.04254800 -0.11517500 C -1.04148700 1.87131900 0.27410100 H -2.65077500 -0.50618200 -0.11517500 C -2.08066900 2.29576900 1.12288800 C 1.74183600 -1.00564900 -0.46752600 C -2.67587800 3.55581000 0.94870500 H 2.65077500 -0.50618200 -0.11517500 C -2.23431900 4.40475900 -0.07676500 H 1.76375400 -2.04254800 -0.11517500 C -1.18603700 3.99382600 -0.91837700 H 1.75969300 -1.01596000 -1.56283200 C -0.58955500 2.73871300 -0.73952300 H 0.00000000 0.00000000 1.95428100 H -1.11733500 -2.76872700 -0.04816700 H -2.41331500 1.63675300 1.92095500 rad_SnMe3_freq: H -0.84141600 4.64663300 -1.71376500 E = -122.9766565 H 0.21379200 2.41605500 -1.39622100 H -3.47821900 3.87005500 1.60864800 H -2.69684700 5.37630400 -0.21794900 C 1.45486600 -3.15477800 -0.48822000 C 2.79950800 -3.16902000 -0.83367500 113 C 1.85227700 1.40704700 0.11031200 C 0.47832300 1.98618100 0.41847400 C 2.72505500 3.73853800 -0.09422600 C 1.40720100 4.23887800 -0.20361200 C 0.31170900 3.41443900 -0.05076300 C 0.88507900 -0.91617400 -0.03181500 0 2 C -0.48936000 -0.28162900 -0.12015000 Sn -0.00024800 -0.00001300 -0.29174500 C -0.67375600 1.04252700 0.06384600 C -2.00032000 -0.15226100 0.49181300 Sn -2.04526800 -1.74588000 -0.28849100 H -1.96279300 -0.12255600 1.58796600 C -2.05572900 1.62222800 0.06952200 H -2.62221500 0.67793100 0.14209400 C -2.59095100 2.22400900 -1.08429400 H -2.47058000 -1.09188200 0.18457700 C -3.90225700 2.71904400 -1.08573800 C 0.86880700 1.80799400 0.49141800 C -4.69411000 2.62228300 0.07080700 H 0.85919200 1.76949300 1.58791400 C -4.16533100 2.03139500 1.22830500 H 1.90457200 1.92128500 0.15562300 C -2.85149700 1.53599500 1.22665000 H 0.30173000 2.68706600 0.16871700 C -1.14273600 -3.41533200 -1.25351300 C 1.13270500 -1.65581200 0.49130700 H -0.77753100 -3.15045100 -2.25254300 H 0.70462600 -2.61043600 0.16905400 H -0.29617700 -3.76212100 -0.64957000 H 2.17391900 -1.61124400 0.15632700 C -2.68467200 -2.30506000 1.66656100 H 1.11681800 -1.61854200 1.58775800 H -3.20282800 -1.47740900 2.16396000 H -1.81537900 -2.59482200 2.26731000 HOCH3_freq: C -3.71065600 -1.03101300 -1.40594900 E = -115.6506207 H -4.26093000 -0.27644600 -0.83067500 H -3.38402600 -0.56887800 -2.34427700 H -1.98020000 2.28339300 -1.98115700 H -4.77170400 1.95369700 2.12510400 H -2.43957300 1.07483800 2.12135800 H -4.30891900 3.16847900 -1.98585700 H -5.71110400 3.00050400 0.06804200 H -0.69476900 3.80926900 -0.14158600 0 1 C 4.25886200 1.80604400 -0.13930500 O 0.04596500 -0.76645800 0.00000000 C 3.38797600 -0.49265100 -0.12633400 H -0.85814900 -1.13080600 0.00000000 C 5.82131500 -0.11526300 -0.31423700 C 0.04596500 0.68244000 0.00000000 C 6.03773100 -1.47857500 -0.38133500 H -0.43934000 1.09226400 0.89466500 C 3.64157400 -1.89521800 -0.18573100 H 1.09332100 0.98330000 0.00000000 C 4.93496900 -2.37579800 -0.31360600 H -0.43934000 1.09226400 -0.89466500 H 7.04451100 -1.87038200 -0.48201700 H 2.81385400 -2.58935900 -0.09580000 rad_OCH3_freq: C 4.49885300 0.40671800 -0.18418500 E = -114.9885405 H 1.25710600 5.29151800 -0.42309500 C 2.97016000 2.32067000 -0.01026200 H 3.57568200 4.40808800 -0.18179900 H -3.37111200 -3.15826300 1.61732400 H -1.85540200 -4.24104200 -1.35923800 H -4.39323900 -1.85564100 -1.64377300

0 2 H 5.11274400 -3.44536900 -0.35435000 O -0.82141300 0.00442700 -0.00002100 H 5.10030900 2.48941400 -0.23293900 C 0.60647800 0.00821500 -0.00002400 H 6.65446000 0.58072300 -0.36267600 H 1.02977700 1.01696500 -0.00074000 O 0.88095500 -1.85745200 1.10517600 H 0.95116600 -0.55007800 0.88203500 C 0.85062400 -1.21619500 2.40356400 H 0.95149500 -0.55159200 -0.88098100 H 1.74732000 -0.60241800 2.55810300 H -0.04587200 -0.58826400 2.51266000 rad_OMe01R_CH03aR_freq H 0.82529700 -2.01996500 3.14039700 E = -1123.082535 H 1.02762900 -1.59326800 -0.88345000 H 0.43136400 2.05460900 1.52964400

rad_OMeH_RR_H: E = -1000.636659

0 2 C 2.05504900 0.04577400 0.00769000

114

0 2 C 1.25404400 -0.43532100 0.02621000

C 0.54750600 0.68063100 0.43611400 0 1 C -0.88957200 0.50191000 0.91394300 C 2.02341200 0.04384600 0.04529800 C 0.38434300 3.14072000 0.80414800 C 1.80395900 1.39885700 0.23146000 C -0.98126600 3.01788100 1.14912100 C 0.41519600 1.96709600 0.48161500 C -1.61906900 1.79433000 1.16734200 C 2.64454800 3.76331200 0.39147500 C 0.52031900 -1.76772100 0.08885600 C 1.40997700 4.27004200 0.20724100 C -0.91471500 -1.60919300 -0.35026100 C 0.25621300 3.36523400 -0.15899200 C -1.62163000 -0.53280500 0.03759500 C 0.85847600 -0.91875300 0.17231000 C -3.06166000 -0.38553900 -0.30824800 C -0.50374200 -0.31159400 -0.09848500 C -3.96022400 -1.43352700 -0.02926300 C -0.69910600 1.01212200 0.06878200 C -5.31245900 -1.33091500 -0.38780800 Sn -2.08277300 -1.74624500 -0.18926300 C -5.78396100 -0.17800900 -1.03248000 C -2.07724800 1.59360500 -0.03446300 C -4.89430200 0.87100200 -1.31809600 C -2.57777500 2.05952700 -1.26472100 C -3.54467300 0.76885400 -0.95716500 C -3.87570100 2.58206200 -1.35385700 H 1.01778200 -2.52585200 -0.52635700 C -4.69081100 2.64300200 -0.21145400 H -3.59357400 -2.31844800 0.48288400 C -4.19970000 2.17968900 1.01916800 H -5.25008700 1.76212700 -1.82517800 C -2.89795600 1.66112200 1.10692300 H -2.85688800 1.57632000 -1.19139500 C -1.11975100 -3.58261600 -0.69312000 H -5.99427100 -2.14435000 -0.16130300 H -0.60549700 -3.51406100 -1.65906700 H -6.83006900 -0.09683300 -1.30965700 H -0.38292200 -3.83247000 0.08048700 H -2.66640500 1.72677600 1.44586000 C -2.98464200 -1.91350300 1.73283800 C 2.48086600 2.10275100 -0.00351500 H -3.76091100 -1.15098600 1.86247600 C 2.62081400 -0.32505500 -0.40941900 H -2.21429900 -1.77199900 2.49854200 C 4.59064400 1.10961300 -0.84060400 C -3.57019500 -1.25113200 -1.63129100 C 5.32367000 0.01007800 -1.23930100 H -4.18662600 -0.42410200 -1.25863300 C 3.40977500 -1.44217600 -0.82234300 H -3.11612000 -0.93553900 -2.57731600 C 4.72361200 -1.28144800 -1.22754200 H 1.01495900 -1.78707500 -0.48386900 H 6.35348800 0.12196800 -1.56132100 H -1.95162600 1.99520700 -2.15034400 H 2.98096900 -2.43803100 -0.82381400 H -4.82683400 2.21706600 1.90431700 C 3.23252300 0.97308700 -0.41609200 H -2.51639000 1.29288900 2.05618100 H -1.54311900 3.91142600 1.40363500 H -4.25327900 2.93164700 -2.30946900 C 1.15597900 1.98594800 0.42064300 H -5.69747600 3.04223800 -0.28144400 H 0.86361500 4.11512800 0.79454300 C 4.19152200 1.85810200 0.02489300 H 2.95002100 3.08411700 -0.02765500 C 3.35420900 -0.44267700 -0.24105700 H 5.30383700 -2.14427300 -1.53816800 C 5.77322700 0.02157000 -0.48654300 H 5.03609100 2.10081100 -0.84305300 C 6.02040000 -1.30655400 -0.77181700 H -0.81766400 -0.01171800 1.89321700 C 3.64539800 -1.80922100 -0.54836600 O 0.46116000 -2.26496700 1.47146300 C 4.93731100 -2.22896700 -0.81093600 C 1.75523700 -2.59398100 2.03336600 H 7.02966900 -1.64978500 -0.97284300 H 2.25730400 -3.36644300 1.43360700 H 2.84521400 -2.53874800 -0.59124400 H 2.40325800 -1.71087200 2.09469200 C 4.44697600 0.48131000 -0.22869300 H 1.56391900 -2.98029000 3.03508800 H 1.23033300 5.33864400 0.28446600 H -1.36229500 -2.38852900 -0.95853900 C 2.90652400 2.32405500 0.21909900 H -3.44069600 -2.90091600 1.86899400 OMeH_RR_4CH2_Sn: H -1.84418100 -4.40290800 -0.75113800 E = -1123.713233 H -4.22084100 -2.11150400 -1.82763000 H 5.12927500 -3.27007700 -1.04950200 H 6.58601200 0.74250500 -0.46307000 H 5.02719600 2.55474400 0.03095800 H 3.49025800 4.40669100 0.62106600 H -0.69275600 3.80432100 0.16320500 H 0.19838100 3.26433200 -1.25419600 H 0.31525100 2.11102400 1.57320800 O 0.69723300 -1.43092400 1.54873700 C 1.74455100 -2.30345000 2.03741200

115 H 1.83453900 -3.20251500 1.41105000 H 2.71255600 -1.79108600 2.07418300 H 1.44595400 -2.59440600 3.04559100

OMeH_RR_4CH2_H: E = -1001.272843

0 1 C 2.01394200 0.00990500 0.11363700 C 1.83051400 1.37867300 0.25285800 C 0.44639500 1.96163700 0.52909500 0 1 C 2.72467700 3.76603500 0.30819900 C -1.24481000 -0.39497200 0.04025700 C 1.35495600 4.18542700 -0.17583100 C -0.55702400 0.78082100 -0.21237000 C 0.31113400 3.34849200 -0.08678500 C 0.94828600 0.80954600 -0.47134400 C 0.83685500 -0.90335900 0.38421500 C -0.51666400 3.27962400 -0.50121600 C -0.50788500 -0.31603600 0.00259100 C 0.81550800 3.32911100 -0.30976700 C -0.68582900 1.01910200 0.11350200 C 1.56996800 2.09491800 0.12800200 Sn -2.10149300 -1.73708700 -0.14828800 C -0.49210500 -1.70689200 -0.06135000 C -2.04343700 1.61359800 -0.06832100 C 0.96540600 -1.57171100 0.27788100 C -2.74933500 1.42253000 -1.27033900 C 1.65305100 -0.44203700 0.03634400 C -4.05574400 1.91383700 -1.41908200 C 3.13427700 -0.41784000 0.20319800 C -4.66878800 2.61067600 -0.36708800 C 3.73332500 -0.93329600 1.36785100 C -3.96222900 2.82529900 0.82873500 C 5.12887000 -0.95150100 1.50855800 C -2.65747200 2.33657000 0.97360200 C 5.94698300 -0.45243400 0.48447300 C -1.20785900 -3.59285900 0.40565100 C 5.35879600 0.06543800 -0.68121700 H -0.54069700 -3.96303400 -0.38231500 C 3.96517000 0.08587100 -0.81770000 H -0.62817500 -3.45222000 1.32513800 H -0.95233800 -2.47890000 0.56815600 C -3.66785100 -1.18528700 1.17852600 H 3.09867100 -1.30479100 2.16735200 H -4.22423600 -0.33278500 0.76983200 H 5.98474500 0.44630600 -1.48181300 H -3.24891800 -0.88894600 2.14646300 H 3.51935700 0.47185600 -1.73111700 C -2.86578100 -1.93089000 -2.13472100 H 5.57383500 -1.34845700 2.41540900 H -3.68568600 -1.22198900 -2.29734800 H 7.02668300 -0.46505500 0.59209600 H -2.08386100 -1.73517800 -2.87770400 C -2.62969900 2.06126000 -0.05975400 H 0.97900600 -1.87213900 -0.11324500 C -2.66030800 -0.37014700 0.32166700 H -2.26328000 0.89908500 -2.08941700 C -4.75879200 0.92764700 0.50957300 H -4.43105300 3.36450700 1.64563500 C -5.45957800 -0.21573700 0.83825700 H -2.12060600 2.49123000 1.90576500 C -3.41606900 -1.53435300 0.66777100 H -4.58764700 1.75705200 -2.35223000 C -4.77376100 -1.46018400 0.92342100 H -5.67986100 2.98854100 -0.47780300 H -6.52520800 -0.17259800 1.03654500 H -0.67093600 3.65045600 -0.43721500 H -2.92550500 -2.49761200 0.74522000 C 4.18142300 1.77991300 -0.21279800 C -3.35557800 0.87865100 0.25380000 C 3.30621000 -0.52096400 -0.23474000 H 1.36210000 4.25988500 -0.43170200 C 5.69085500 -0.11047900 -0.75517500 C -1.26366100 2.03367900 -0.26205100 C 5.90427900 -1.46164200 -0.93866800 H -5.32325700 -2.35673200 1.19146900 C 3.56395900 -1.91682400 -0.42775900 H -5.26476300 1.88733000 0.44701300 C 4.82250400 -2.37325800 -0.77274800 H -3.16422600 3.00758200 -0.11001100 H 6.88670800 -1.83378500 -1.20911300 H -1.08249000 4.16444700 -0.78147200 H 2.76513900 -2.63978000 -0.31067200 H 2.62015000 2.17096600 -0.16317300 C 4.39954000 0.38601800 -0.40317500 H 1.55797400 2.02009300 1.22667100 H 1.23600400 5.17833300 -0.59976600 H 1.08416800 0.85868800 -1.56619800 C 2.93679500 2.27717200 0.11095100 O -0.47934200 -2.19930900 -1.44987900 H -4.36481700 -2.01603500 1.33688000 C -1.76025300 -2.62381000 -1.97444000 H -1.97190900 -4.35732700 0.58759200 H -2.19675300 -3.42129000 -1.35645200 H -3.24834100 -2.94509900 -2.29869300 H -2.46987000 -1.79025800 -2.03761400 H 4.99105100 -3.43515800 -0.91959000 H -1.56036000 -3.01088400 -2.97451900 H 6.50383600 0.59993700 -0.87858100 H 1.48379700 -2.47601000 0.58411400 H 5.02163100 2.46038700 -0.33446800 H 3.51069000 4.32588800 -0.20822400 OMeH_RR_6CH2_Sn: H 2.82102100 4.00897000 1.37785900 E = -1123.706912 H 0.35966100 2.07522100 1.62642100 O 0.69167900 -1.16813700 1.82949600 C 1.76867100 -1.93923900 2.41646800

116 H 1.86469700 -2.91863400 1.92560600 H 2.72594200 -1.40861400 2.34826800 H 1.50285700 -2.08370500 3.46456000

OMeH_RR_6CH2_H: E = -1001.2655302

0 1 C 1.99878600 0.05452400 0.14730900 C 1.79687200 1.39674300 0.27375800

0 1 C 0.41870900 1.99057500 0.51192000 C 1.23766900 -0.40770300 -0.01511600 C 2.71478900 3.63179400 -0.16998300 C 0.55666000 0.77036000 0.25575300 C 1.35558800 4.13733300 -0.39091500 C -0.95935100 0.80768900 0.45197400 C 0.27993800 3.37707600 -0.09906700 C 0.47893300 3.27851800 0.64381500 C 0.83206900 -0.88294500 0.36178000 C -0.86148100 3.24542300 -0.06021300 C -0.52272800 -0.29631800 0.01345100 C -1.52469500 2.08445300 -0.16648500 C -0.71400800 1.03643400 0.12070400 C 0.48232400 -1.71829800 0.07313200 Sn -2.10796300 -1.72936800 -0.13424200 C -0.97721800 -1.58263300 -0.25528100 C -2.07665000 1.62353500 -0.04415700 C -1.66416500 -0.44554700 -0.04757100 C -2.69262900 2.32268200 1.01283200 C -3.14536900 -0.41492800 -0.20453200 C -4.00007700 2.80798200 0.87952400 C -3.77401100 -1.11542800 -1.25276600 C -4.70773700 2.61201200 -0.31875600 C -5.17020900 -1.12415400 -1.37418700 C -4.09346700 1.93738700 -1.38438400 C -5.96348400 -0.42711300 -0.45025400 C -2.78396200 1.45067100 -1.24775700 C -5.34711100 0.28351300 0.59203400 C -1.20705900 -3.59848800 0.35572300 C -3.95137400 0.29377200 0.70923500 H -0.54568600 -3.94149800 -0.44934800 H 0.93799900 -2.48241100 -0.56955000 H -0.61977500 -3.48595600 1.27361500 H -3.16261900 -1.63528400 -1.98453100 C -3.65531500 -1.20441400 1.22527100 H -5.95165500 0.82758100 1.31051000 H -4.21787100 -0.34534800 0.83944400 H -3.48623200 0.84678000 1.52077200 H -3.22290800 -0.92505400 2.19231800 H -5.63710900 -1.66481100 -2.19131400 C -2.90400200 -1.88572400 -2.11217400 H -7.04447800 -0.43166200 -0.54420000 H -3.72655500 -1.17459800 -2.24920100 H -2.47479200 2.02338700 -0.68729000 H -2.13406900 -1.67652800 -2.86407600 C 2.61445700 2.05343200 0.08119000 H 0.98423800 -1.82061500 -0.18965600 C 2.64777400 -0.37843800 -0.30943200 H -2.15683800 2.45828700 1.94877300 C 4.73536200 0.92928400 -0.54093000 H -4.62720100 1.79336500 -2.31852000 C 5.43531100 -0.21061300 -0.88154400 H -2.29791500 0.94281400 -2.07638500 C 3.40369700 -1.54065500 -0.66795500 H -4.47039900 3.32838900 1.70765300 C 4.75472000 -1.45975200 -0.94986900 H -5.72126400 2.98583300 -0.42029000 H 6.49653900 -0.16234500 -1.10139200 H -0.72548600 3.76119200 -0.24244200 H 2.91635500 -2.50640900 -0.73451400 C 4.30042200 1.76335700 0.42912600 C 3.33795800 0.87323400 -0.25495600 C 3.33580300 -0.47926700 -0.22562400 H -1.25627700 4.16223300 -0.48705300 C 5.73129000 -0.09767400 -0.51905700 C 1.25926300 2.01670400 0.32581700 C 5.90435400 -1.40553900 -0.99622900 H 5.30412200 -2.35374600 -1.22658100 C 3.52423400 -1.79204400 -0.70674200 H 5.23773400 1.89153500 -0.48935100 C 4.79155200 -2.25206100 -1.08846900 H 3.15050800 2.99895100 0.12643500 H 6.88730800 -1.75431100 -1.29465500 H 1.05645600 4.16252600 0.35876500 H 2.68413100 -2.46957600 -0.80724800 H 0.31785800 3.34302900 1.73132800 C 4.46860200 0.36730400 -0.13462700 H -1.13693500 0.86016800 1.54266200 H 1.22885300 5.13926900 -0.78874800 O 0.47719200 -2.22998700 1.45527300 C 2.93057300 2.33274200 0.15380300 C 1.75893300 -2.67167800 1.96316200 H 3.55508500 4.31085600 -0.28868000 H 2.18119300 -3.46774900 1.33353600 H -4.34950600 -2.03837200 1.37859300 H 2.47724100 -1.84560400 2.02668100 H -1.96889200 -4.36968300 0.51771100 H 1.56525000 -3.06609800 2.96160100 H -3.28833300 -2.89747000 -2.28753600 H -1.49624400 -2.49683100 -0.52882500 H 4.90616700 -3.26470200 -1.46099300 H 6.58593000 0.56995000 -0.44544100 OMeH_RR_7CH2_Sn: H 4.43569000 1.70816500 1.52196200 E = -1123.680079 H 5.08051500 2.43016300 0.04742500 H 0.31420500 2.12939700 1.60848700 O 0.69539400 -1.24402800 1.78705200 C 1.80799600 -2.00765000 2.31566600 117 H 1.97056200 -2.92366000 1.72875900 H 2.73244000 -1.41768100 2.31733000 H 1.53892800 -2.27219100 3.33930600

OMeH_RR_7CH2_H: E = -1001.238381

0 1 C 1.94557500 0.06814700 0.31312300 C 1.70895100 1.41222600 0.36192500 C 0.36286800 1.91127400 0.86757100 C 2.43516200 3.71392000 -0.11667400 0 1 C 1.11640600 4.21861800 0.23702100 C 1.18731300 -0.37985700 0.01288700 C 0.13362800 3.38764200 0.66029100 C 0.51657600 0.78020400 0.25839800 C 0.82218000 -0.84176700 0.77804700 C -0.99043000 0.85956100 0.42709500 C -0.54310500 -0.34780100 0.31739700 C 0.63037800 3.22707700 0.07596300 C -0.77289600 0.98205100 0.39110200 C -0.78477900 3.24465300 -0.31589000 Sn -1.98451300 -1.78922500 -0.31452900 C -1.54699600 2.13837700 -0.19010100 C -2.11712700 1.55745400 0.09379600 C 0.43575800 -1.69357500 0.01749600 C -3.22082400 1.20963100 0.89547600 C -1.03661600 -1.54106600 -0.24051200 C -4.50668600 1.68032300 0.58564700 C -1.71428500 -0.39893300 -0.03225800 C -4.70077100 2.50708700 -0.53038900 C -3.19853300 -0.36522100 -0.15225600 C -3.60081300 2.87183600 -1.32673400 C -3.98391400 0.31916000 0.79717600 C -2.31740900 2.40600300 -1.01251100 C -5.38198400 0.30934800 0.71190100 C -0.83001300 -3.50561200 -0.84642700 C -6.02126500 -0.37643000 -0.33353400 H -0.01687200 -3.23720400 -1.53181700 C -5.24870200 -1.04949100 -1.29188600 H -0.39268800 -3.96833100 0.04678800 C -3.84988000 -1.04100000 -1.20261200 C -3.29874300 -2.32295900 1.27919500 H 0.86364700 -2.39468700 -0.71146500 H -4.19783500 -1.69640900 1.26270300 H -3.50152200 0.84652400 1.61592500 H -2.79320100 -2.18572600 2.24180700 H -5.73349800 -1.57211900 -2.11033500 C -3.08924200 -1.06755100 -1.98295200 H -3.25417200 -1.54264100 -1.95955500 H -3.73719000 -0.23781300 -1.67485500 H -5.97049900 0.83226500 1.45882300 H -2.41323400 -0.69948200 -2.76273100 H -7.10414400 -0.38154800 -0.40200500 H 0.99129800 -1.86993500 0.43638200 H -2.59369500 2.14636800 -0.47753700 H -3.06201100 0.57633000 1.76478700 C 2.70779000 1.95282700 0.74524200 H -3.74627200 3.51091200 -2.19176800 C 2.64631100 -0.35546500 -0.27947900 H -1.46799700 2.68038200 -1.63190400 C 4.76599800 0.85775100 -0.25189800 H -5.34933900 1.40275500 1.21100400 C 5.41531400 -0.22070800 -0.87145000 H -5.69433000 2.86723200 -0.77677300 C 3.31032900 -1.43064300 -0.90561300 H -0.84502100 3.77765700 0.92520700 C 4.67850500 -1.36696100 -1.20013600 C 4.00597000 1.83893300 -0.49008300 H 6.47473800 -0.16471800 -1.09859500 C 3.22981000 -0.46914600 -0.15330800 H 2.76521900 -2.32562600 -1.18364600 C 5.65818600 0.01819900 -0.93532700 C 3.39921900 0.80053800 0.04387600 C 5.78254000 -1.47550100 -1.09739100 H -1.20578300 4.16231100 -0.71460200 C 3.49655800 -1.81274700 -0.26561600 C 1.25720100 2.05602800 0.34781900 C 4.77215700 -2.31169600 -0.76934500 H 1.18233400 4.16268300 0.10926800 H 6.72608300 -1.86328000 -1.47180300 H 5.16445500 -2.20613000 -1.68707700 H 2.74676400 -2.55096600 -0.00378800 H 5.32602400 1.75375600 0.00260600 C 4.27376000 0.50613900 -0.52608300 H 2.75863900 1.77444900 1.83175200 H 0.92751100 5.28404100 0.15047400 H 3.23257500 2.89387400 0.55132000 C 2.72069000 2.37268700 -0.07175500 H -1.17936600 0.94293800 1.51746500 H 3.19602900 4.41393300 -0.45164600 O 0.49575700 -2.34087400 1.33928500 H 4.77261600 2.55368600 -0.78650800 C 1.80506900 -2.81231400 1.74016700 H -3.60673400 -3.37148100 1.19555900 H 2.22661300 -3.49704400 0.99048900 H -1.45750900 -4.25539700 -1.34188200 H 2.50476100 -1.98256100 1.89496000 H -3.71464100 -1.85989500 -2.41030300 H 1.65676300 -3.34774300 2.67890700 H 4.89396400 -3.38499600 -0.87979300 H -1.56939700 -2.45653200 -0.48334700 H 5.96112000 0.51436000 -1.86747100

H 6.38976800 0.34754900 -0.18096500 OMeH_RR_8CH2_Sn: H 0.36608500 1.74848100 1.96363200 E = -1123.645361 O 0.73257200 -0.87283500 2.24755500 C 1.91305900 -1.40951800 2.89408100

118 H 2.11802400 -2.43261400 2.54803400 H 2.79390600 -0.78496600 2.69992600 H 1.69754000 -1.42212300 3.96326300

OMeH_RR_8CH2_H: E = -1001.2041399

0 1 C 1.94612800 0.09153400 0.31214700 C 1.69920700 1.43155500 0.36043300 C 0.34918900 1.91662800 0.87261900 0 1 C 2.39837000 3.74558600 -0.11241800 C 1.20552300 -0.44770400 0.03444100 C 1.07579000 4.23533400 0.25228100 C 0.51208000 0.65394500 0.44798900 C 0.10412400 3.39182100 0.67417900 C -0.93231800 0.49512300 0.90989100 C 0.83336100 -0.82854900 0.78110100 C 0.40876300 3.08450300 0.81756500 C -0.53715000 -0.34861300 0.32037700 C -0.99998000 2.98749800 1.17204500 C -0.77888900 0.97904000 0.39551600 C -1.64523700 1.79631600 1.17777300 C -2.12717000 1.54358700 0.09623200 C 0.46342100 -1.77523300 0.07751800 C -3.23021500 1.18704200 0.89492800 C -0.96742200 -1.60186900 -0.37213300 C -4.51867700 1.64883900 0.58231600 C -1.67020400 -0.52643200 0.02527100 C -4.71599300 2.47510100 -0.53353900 C -3.10932900 -0.36754900 -0.31895200 C -3.61677900 2.84839700 -1.32696300 C -4.01353400 -1.41462500 -0.05558100 C -2.33085400 2.39163400 -1.00988700 C -5.36442900 -1.30088800 -0.41601000 H 1.01322200 -1.85538200 0.43944500 C -5.82876000 -0.13752600 -1.04691100 H -3.06896900 0.55430900 1.76422900 C -4.93341700 0.91109700 -1.31614300 H -3.76473500 3.48718700 -2.19178400 C -3.58538800 0.79789200 -0.95295100 H -1.48178600 2.67280600 -1.62671000 H 0.96106700 -2.53225900 -0.53876500 H -5.36086100 1.36499700 1.20550000 H -3.65195700 -2.30792700 0.44547600 H -5.71148900 2.82841600 -0.78196600 H -5.28388600 1.81061600 -1.81201800 H -0.87754600 3.76984500 0.94545600 H -2.89342200 1.60568800 -1.17327300 C 3.98486800 1.89314500 -0.51474200 H -6.05077600 -2.11389900 -0.20189800 C 3.23923700 -0.43840000 -0.16065300 H -6.87373200 -0.04768900 -1.32569800 C 5.55862900 0.06619500 -1.02257700 H -2.69565200 1.73720200 1.44821400 C 5.84974200 -1.24747200 -1.09574500 C 2.51860700 2.06111800 0.02768800 C 3.53845300 -1.76666100 -0.22900900 C 2.60415900 -0.35773900 -0.39941300 C 4.85723300 -2.31449600 -0.71252700 C 4.66540000 1.15069000 -0.87037900 H 6.82625100 -1.57543900 -1.44254600 C 5.37601800 -0.13167600 -1.22162400 C 4.25534600 0.55952500 -0.56410500 C 3.35127500 -1.44716000 -0.77701700 H 6.29788100 0.81052500 -1.30966500 C 4.74888600 -1.32861800 -1.17996800 H 0.87603100 5.29933100 0.17323700 H 6.41660100 -0.06052500 -1.52643100 C 2.69973600 2.40957300 -0.07677200 H 2.91819600 -2.44117800 -0.77808100 H 3.14864000 4.45553500 -0.45055900 C 3.22832300 0.97973000 -0.39224100 H 4.74297100 2.61031700 -0.82443500 H -1.53517500 3.89621900 1.42875300 H 5.29397700 -2.96325400 0.06334500 C 1.13330100 1.97592100 0.45870200 H 4.68470500 -2.98201900 -1.57212100 H 0.88483300 4.06143800 0.81167000 H 2.80619800 -2.51157600 0.06914200 H 2.98472100 3.04562400 0.03330000 H 0.35736600 1.74924100 1.96769000 H 5.28370100 -2.23437000 -1.44864400 O 0.74262200 -0.85934700 2.25089900 H 4.67455000 1.80805100 -1.75290700 C 1.93268600 -1.36786700 2.90173200 H 5.24283700 1.68666000 -0.10399900 H 2.15337100 -2.39257700 2.56986700 H -0.87863000 -0.02351600 1.88744000 H 2.80268500 -0.73149700 2.69760200 O 0.37776300 -2.28629900 1.45486100 H 1.71946900 -1.36989900 3.97148900 C 1.66070900 -2.59027800 2.05445000 Sn -1.96449200 -1.80104500 -0.31606900 H 2.19658400 -3.35189300 1.47055200 C -0.79422000 -3.50633500 -0.85047000 H 2.28850300 -1.69412200 2.13385200 H -1.41339600 -4.25894500 -1.35204500 H 1.44683900 -2.98057100 3.05026800 H 0.01965700 -3.22784900 -1.53098000 H -1.41599500 -2.37237900 -0.99076100 H -0.35693600 -3.96916200 0.04268100 C -3.27712900 -2.35022500 1.27359600 OMeH_RR_10CH2_Sn: H -4.17956200 -1.72843900 1.25870400 E = -1123.648838 H -3.57926400 -3.40000300 1.18466200 H -2.77370900 -2.21449200 2.23752300 C -3.07342800 -1.08588600 -1.98458500 H -3.69123300 -1.88272000 -2.41463000 H -3.72905400 -0.26269800 -1.67507800 119 H -2.39982600 -0.70970900 -2.76257200

OMeH_RR_10CH2_H: E = -1001.206328

0 1 0 1 C 1.99935200 0.12117400 0.07981200 C -1.20305000 -0.38695200 -0.00539500 C 1.78716000 1.45642400 0.16412800 C -0.51335900 0.75857000 -0.27694900 C 0.40339600 2.06166400 0.32563500 C 0.96442300 0.70424700 -0.67073800 C 2.69081500 3.74470500 -0.01372700 C -0.46151700 3.22646700 -0.35476000 C 1.36702000 4.24034900 -0.38501300 C 0.98979400 3.20565300 -0.45797600 C 0.28140200 3.43870500 -0.30128700 C 1.66834800 2.03959100 -0.55007100 C 0.85043700 -0.85580200 -0.05253800 C -0.45477100 -1.70075800 -0.11751600 C -0.53023700 -0.23503200 -0.13463900 C 0.98136700 -1.56742100 0.31547300 C -0.72743900 1.09144600 0.01413500 C 1.68495900 -0.46212100 0.01819900 Sn -2.10237900 -1.68787600 -0.15647500 C 3.15147700 -0.40334900 0.26659600 C -2.11665100 1.65491300 0.04464400 C 4.04554800 -0.11253400 -0.78342800 C -2.86272300 1.60462200 1.23675900 C 5.42844200 -0.10773100 -0.56325600 C -4.17857700 2.09253300 1.27577200 C 5.94020900 -0.38743800 0.71478900 C -4.75909700 2.64142600 0.12206700 C 5.05794700 -0.67584900 1.76616800 C -4.01799200 2.70014100 -1.06981800 C 3.67270200 -0.68361900 1.54290400 C -2.70473200 2.21080800 -1.10635900 H -0.94940500 -2.49222700 0.45707800 C -1.32847200 -3.45665500 -1.07695200 H 3.65531700 0.08147600 -1.77947400 H -0.53757200 -3.22784500 -1.80216300 H 5.44566200 -0.88914400 2.75722800 H -0.92057200 -4.13781100 -0.32186900 H 2.98624000 -0.89321900 2.35797200 C -2.68589500 -2.12101600 1.84373000 H 6.10471900 0.10743500 -1.38436500 H -3.39230200 -1.37121500 2.21727900 H 7.01149800 -0.38060000 0.88695400 H -1.79044500 -2.11382300 2.47437100 H 2.75211800 2.04199900 -0.59227800 C -3.78930700 -1.03768900 -1.28383100 C -2.61023700 2.08343000 0.02040700 H -4.33055100 -0.25021600 -0.74545500 C -2.64207300 -0.36480600 0.33184200 H -3.48071000 -0.63317100 -2.25454600 C -4.75210700 1.00063800 0.57975200 H 1.00957300 -1.48155500 -0.94824200 C -5.46242300 -0.09783400 0.90206400 H -2.41078500 1.17285300 2.12657200 C -3.36350700 -1.47511100 0.65436600 H -4.46467700 3.11560200 -1.96734600 C -4.83284200 -1.46383700 0.99268400 H -2.13532600 2.23725200 -2.03157100 H -6.52631400 -0.02310700 1.11165400 H -4.74657800 2.04217000 2.19924800 C -3.31381300 0.95192600 0.29525800 H -5.77721800 3.01579000 0.14959000 H -5.23551100 1.97338400 0.52657400 H -0.70473100 3.79516400 -0.58047300 H 1.52780700 4.14785600 -0.43107600 C 4.25967200 1.87583100 0.34348500 C -1.18020400 2.06758400 -0.23091300 C 3.39113500 -0.48009100 0.20718600 H -0.97565200 4.18276000 -0.30793900 C 5.87053500 0.00109900 0.26236400 H -3.11641800 3.04696500 0.01145400 C 6.11581700 -1.20368400 -0.31657700 H -5.36747600 -2.16106700 0.32796400 C 3.73989300 -1.56517100 -0.80852400 H -4.98100200 -1.87149800 2.00556300 C 5.02823400 -1.92951500 -0.99118800 H -2.88837200 -2.45094200 0.68632000 H 7.12537700 -1.59852200 -0.36980400 H 0.97365900 0.44508100 -1.74919400 C 4.50873000 0.54530200 0.28373900 O -0.36763400 -2.14211900 -1.52097900 H 6.68175600 0.61392300 0.64702600 C -1.64126700 -2.43723900 -2.14345800 H 1.27644300 5.25768800 -0.75220000 H -2.18038900 -3.21826600 -1.58855000 C 2.91349300 2.41413000 0.20641300 H -2.27458600 -1.54406000 -2.20748700 H 3.52989000 4.43563200 -0.00710600 H -1.41066300 -2.79844000 -3.14663400 H 5.08594300 2.58032100 0.42530600 H 1.46556200 -2.43648100 0.74981100 H -3.16159100 -3.10614500 1.91163300 H -2.13071200 -3.97944500 -1.61103400 OMeH_RR_11aCHR_Sn: H -4.47508500 -1.87570300 -1.45867300 E = -1123.625058 H 5.28491900 -2.74012600 -1.66623400 H 2.94241700 -2.07576400 -1.33962000 H 3.40225600 -0.99143200 1.19355800 H 0.30463200 2.25357700 1.41633200 O 0.76560500 -1.78050600 1.09773200 C 1.47523800 -3.04115500 0.99598300 H 1.36199200 -3.47830200 -0.00575000 H 2.54232100 -2.93119200 1.21902400 120 H 1.01822200 -3.70663000 1.73166300

OMeH_RR_11aCHR_H: E = -1001.188887

0 1 C -1.22535500 -0.28992800 -0.00870600 0 2 C -0.57515200 0.89157200 -0.10411000 C 2.02321000 0.04246400 -0.02978500 C 0.93522400 1.00373700 -0.25284200 C 1.78601500 1.42125300 0.13299900 C -0.66319400 3.34790500 0.04748700 C 0.44499300 1.94228900 0.17340100 C 0.73162900 3.36147700 0.48772500 C 2.65739600 3.76470500 0.42392600 C 1.48772900 2.24145400 0.43602400 C 1.41297200 4.26464900 0.53995500 C -0.48560600 -1.58573000 0.19870600 C 0.18009800 3.41072900 0.41904300 C 1.01034700 -1.43906000 0.24897500 C 0.85969000 -0.91722400 0.08564500 C 1.67560200 -0.28354200 0.05803200 C -0.50272600 -0.30688500 -0.14473100 C 3.16595100 -0.25545900 0.06317100 C -0.66409300 1.05963100 -0.04812100 C 3.87506400 0.57279500 -0.83040300 Sn -2.09086500 -1.73258500 -0.12877700 C 5.27548100 0.56314700 -0.85949900 C -2.04739300 1.63240200 -0.13943100 C 5.99544300 -0.26597200 0.01478800 C -2.50742500 2.20995000 -1.33710700 C 5.30078400 -1.08078600 0.92164000 C -3.81932700 2.69480800 -1.43610900 C 3.89995300 -1.07181100 0.94660700 C -4.68632500 2.61058100 -0.33376000 H -0.82344200 -2.05019900 1.14369800 C -4.23214500 2.04350000 0.86696000 H 3.33244400 1.21993900 -1.51376200 C -2.91775100 1.55889300 0.96312500 H 5.84851200 -1.71259900 1.61347600 C -1.15799900 -3.57023700 -0.67971200 H 3.36906600 -1.68151800 1.67190500 H -0.70367400 -3.50655000 -1.67549500 H 5.80326600 1.20023200 -1.56173900 H -0.37536900 -3.81139400 0.05019900 H 7.08019400 -0.27013900 -0.00464300 C -2.90973900 -1.91242900 1.82987400 H 2.50515300 2.22165500 0.81347900 H -3.72955900 -1.20086400 1.97818600 C -2.76720000 2.09930500 -0.31264800 H -2.11892800 -1.70960400 2.56007100 C -2.72029200 -0.41301800 -0.24323900 C -3.62473300 -1.21034800 -1.51113100 C -4.90565800 0.87179600 -0.23463700 H -4.17034900 -0.33013100 -1.14831100 C -5.54920600 -0.22052300 0.25418400 H -3.20213200 -0.96728700 -2.49252100 C -3.45023000 -1.43784800 0.61175500 H 1.00649900 -1.77758200 -0.58489700 C -4.78727900 -1.36000500 0.78665800 H -1.83945400 2.25577400 -2.19315900 H -6.63283300 -0.24024400 0.31675600 H -4.89656000 1.97681000 1.72267800 C -3.44221800 0.92184000 -0.27095800 H -2.56066600 1.11824400 1.89078800 H -5.45894100 1.75822200 -0.53488000 H -4.16815300 3.12593000 -2.36906000 H 1.13256400 4.28007300 0.90515200 H -5.70327200 2.98116000 -0.41145000 C -1.31839500 2.16767200 -0.17746700 C 4.18980200 1.86617700 0.02766200 H -1.21868500 4.28174900 0.02622600 C 3.35644100 -0.43655200 -0.28057100 H -3.31814600 3.03683600 -0.36695400 C 5.77839800 0.03400200 -0.47808100 H -5.32061300 -2.13437500 1.32925100 C 6.03391400 -1.29335300 -0.77105800 H -2.89378200 -2.29225700 0.98443500 C 3.65670900 -1.80085700 -0.59430300 H -2.79936100 -0.83324300 -1.26783200 C 4.95395900 -2.21636400 -0.83836700 H 1.08044800 1.18948800 -1.33779100 H 7.04757000 -1.63243600 -0.95625100 O -0.91384000 -2.47585500 -0.88592700 H 2.85711300 -2.52934600 -0.66045800 C -0.55195000 -3.86339100 -0.70406100 C 4.45050800 0.48957000 -0.24160600 H 0.52187900 -4.02380300 -0.85704600 H 1.26076200 5.32572800 0.71881200 H -0.83155700 -4.21275800 0.30156400 C 2.90711900 2.33767300 0.19294700 H -1.10861000 -4.42837100 -1.45233800 H -3.29373900 -2.92496400 1.99950300 H 1.57433200 -2.35562700 0.41535300 H -1.88237400 -4.39255100 -0.68801400 H -4.33624400 -2.03543100 -1.63350200 rad_OMe_4CH2_Sn: H 5.15120900 -3.25477400 -1.08429900 E = -1123.0914501 H 6.59026800 0.75488400 -0.43263100 H 5.02891500 2.55692900 0.07806800 H 3.52468300 4.41560200 0.50087400 H -0.43423800 3.52041900 1.32860700 H -0.46094800 3.81032100 -0.38185200 O 0.70436700 -1.46722800 1.46103500 C 1.75846400 -2.33764300 1.94100600

121 H 1.86177100 -3.22613000 1.30179200 H 2.72073700 -1.81687000 1.99465500 H 1.45423500 -2.64709700 2.94223800 rad_OMe_4CH2_H: E = -1000.647223

0 1 C 2.07578200 -0.15493700 0.00014800 C 1.90848100 1.25689800 0.03117300 C 0.60073100 1.82508200 0.03004300 0 2 C 2.89772100 3.56994200 0.14114100 C 1.23472800 -0.39208900 -0.11821900 C 1.67623100 4.13466400 0.14985400 C 0.52122100 0.78672500 0.17666100 C 0.40371600 3.33329000 0.07340600 C -0.91855500 0.79076900 0.24068600 C 0.91537400 -0.96847500 -0.00471300 C 0.50906900 3.23692400 0.75175800 C -0.37405100 -0.43361800 0.01081200 C -0.82539900 3.23675800 0.92720100 C -0.51950100 0.98468600 0.01630600 C -1.67568500 2.01645500 0.69820700 Sn -2.03546200 -1.78474500 -0.01508500 C 0.49053400 -1.70975100 -0.08051400 C -1.90241400 1.55942300 0.00385600 C -0.97162600 -1.56581400 -0.36885700 C -2.41826700 2.16899700 -1.15567500 C -1.64174400 -0.39125000 -0.14447000 C -3.73516700 2.64771200 -1.18601300 C -3.13031800 -0.36930300 -0.29089200 C -4.55652500 2.52386300 -0.05283900 C -3.75253700 0.41303700 -1.28251600 C -4.04995900 1.92274600 1.10930500 C -5.14569800 0.39737200 -1.43307900 C -2.72984900 1.44496000 1.13633700 C -5.93654300 -0.39987800 -0.58856800 C -1.18809600 -3.67224500 -0.53600700 C -5.32436100 -1.18447700 0.39967800 H -0.60852800 -3.60099000 -1.46366400 C -3.92840400 -1.17030200 0.54590400 H -0.52697300 -4.03968600 0.25787100 H 0.93954000 -2.44319900 -0.76298000 C -2.92842600 -1.95028900 1.91664600 H -3.13850300 1.01294300 -1.94976800 H -3.72515400 -1.20707300 2.03244000 H -5.92988800 -1.80492200 1.05265700 H -2.18367500 -1.79016700 2.70445100 H -3.44746800 -1.77428300 1.31017100 C -3.50508100 -1.19329600 -1.43316900 H -5.61251200 0.99683700 -2.20814100 H -4.08928400 -0.35306600 -1.03821300 H -7.01555800 -0.41142700 -0.70404200 H -3.04038000 -0.87246800 -2.37194400 C 2.60618700 2.06737000 0.16508800 H 1.03159800 -2.04814700 -0.02295700 C 2.64771100 -0.34098500 -0.37337400 H -1.79146200 2.23910300 -2.04099100 C 4.73774000 0.97935800 -0.47895000 H -4.67684900 1.82722500 1.99038500 C 5.44873700 -0.14001300 -0.87166700 H -2.33411600 0.98371600 2.03794400 C 3.41448500 -1.47907600 -0.78176800 H -4.12365200 3.10357700 -2.09099100 C 4.77235500 -1.38157900 -1.02937600 H -5.57773600 2.88991700 -0.07703000 H 6.51456500 -0.07731000 -1.06344400 C 4.33799100 1.56623600 0.06300600 H 2.92884700 -2.43856800 -0.91669900 C 3.42289000 -0.73026200 -0.02108600 C 3.33745500 0.90829400 -0.23090700 C 5.85995000 -0.39278600 -0.01033100 H -1.34009000 4.14268800 1.23600100 C 6.06903700 -1.76321800 -0.06121500 C 1.24331700 2.02950500 0.35898900 C 3.66311800 -2.12783500 -0.07408900 H 5.32818000 -2.25801800 -1.34653100 C 4.95625100 -2.63759900 -0.09402800 H 5.23820600 1.93632900 -0.35848500 H 7.07648500 -2.16527400 -0.07691300 H 3.14369900 3.00320200 0.30261000 H 2.83231900 -2.82312600 -0.10361000 H 1.08821000 4.14300600 0.91055300 C 4.54567200 0.14329900 0.00956900 H -2.22533400 1.77043200 1.62281300 H 1.57162000 5.21528500 0.20457300 H -2.46825200 2.26466000 -0.02133800 C 3.08372700 2.11620000 0.07344500 O 0.51062400 -2.29772900 1.28181400 H -3.36289100 -2.94753200 2.05221800 C 1.80004500 -2.76256400 1.74961300 H -1.97813700 -4.41710400 -0.68561500 H 2.21430500 -3.52647300 1.07622900 H -4.18836900 -2.02278800 -1.64950100 H 2.51877200 -1.94064400 1.84632600 H 5.11368400 -3.71026300 -0.13562900 H 1.61840900 -3.20595800 2.72983700 H 6.70341800 0.29177400 0.01443300 H -1.51640900 -2.46037200 -0.65404900 H 5.21150300 2.21412200 0.09631000 H 3.79281300 4.18499900 0.18894600 CH2_04: H -0.24384100 3.58723500 0.92575900 E = -1008.083862 H -0.16532300 3.65736100 -0.80933000

benzoanthra_4H_3Ph: E = -885.6447705

122 0 2 C 2.07982000 -0.12855200 0.04777900 C 1.91381600 1.28698600 0.06178100 C 0.59983700 1.86178000 0.08833000 C 2.88296500 3.56410400 0.08922400 C 1.59623400 4.11208800 0.13921100 C 0.46965700 3.28646600 0.14172900 C 0.92146800 -0.93419400 0.06663700 C -0.38392100 -0.39842100 0.08453500 C -0.54386000 1.00140800 0.08736200 Sn -2.02765000 -1.77083500 -0.04074700 C -1.92310300 1.57574200 0.05946100 C -2.80756000 1.35875800 1.13240900 C -4.12965000 1.82755300 1.07597300 C -4.58172800 2.52261100 -0.05589600 0 1 C -3.70128000 2.75557300 -1.12600100 C 1.31038700 -0.70310800 0.03546900 C -2.38147800 2.28850900 -1.06591800 C 0.65141200 0.55892600 -0.01655700 C -1.12910500 -3.62776500 -0.58782600 C -0.77330700 0.63710900 -0.00156400 H -0.50556900 -3.51688500 -1.48258200 C 0.76858500 3.06809400 -0.21944400 H -0.50368300 -4.01700000 0.22456500 C -0.57264500 3.17068000 -0.21841000 C -3.00837100 -2.03621500 1.83599000 C -1.48319700 1.98128200 -0.06689400 H -3.85670400 -1.34871100 1.92600700 C 0.51584100 -1.87465900 0.06819500 H -2.31802900 -1.84940700 2.66635200 C -0.86777800 -1.79300700 0.06055300 C -3.41123200 -1.13293800 -1.52299900 C -1.52871300 -0.54224500 0.03793700 H -2.88295800 -0.79225700 -2.42041000 H -2.21393100 1.96305400 -0.88868500 H -4.08460600 -1.95036300 -1.80550000 C 2.81858400 1.70222700 -0.10415900 H 1.03353800 -2.01423700 0.05033600 C 2.77327400 -0.76470200 0.04592800 H -2.45241400 0.83344700 2.01544600 C 4.93449200 0.40854400 -0.01091300 H -4.04437700 3.29150700 -2.00511700 C 5.61323400 -0.79888800 0.06327700 H -1.70311800 2.45357000 -1.89855400 C 3.49026400 -1.98676600 0.12225100 H -4.79982100 1.65335300 1.91193100 C 4.88015400 -2.00814600 0.13077900 H -5.60473300 2.88132000 -0.10349400 H 6.69779200 -0.82064900 0.07035400 H -0.52104700 3.72345800 0.20084800 C 3.51558200 0.44666700 -0.02027600 C 4.35763200 1.58743400 0.02188600 H 5.48218900 1.34553200 -0.06317400 C 3.42733000 -0.70056500 0.00979900 H -1.04933400 4.14286000 -0.31361400 C 5.87329300 -0.36560300 -0.04256500 C 1.45123200 1.77463200 -0.10457200 C 6.07714000 -1.73429000 -0.06754300 H 1.39225000 3.95324600 -0.31570700 C 3.66854100 -2.09748200 -0.01628900 H 3.40617400 2.61540400 -0.17280700 C 4.96070100 -2.60921300 -0.05420500 H 5.40607100 -2.95523800 0.19125700 H 7.08289000 -2.13969400 -0.09787400 H 2.95684000 -2.92840500 0.17904400 H 2.83719400 -2.79278600 -0.00866100 H -1.46776200 -2.69787100 0.08805500 C 4.55548700 0.17977800 -0.00385300 H -2.08994200 2.12554000 0.83776300 H 1.47067900 5.18901000 0.18120000 C -3.02355600 -0.53523800 0.03596900 C 3.06993300 2.15422200 0.05587600 C -3.75464100 0.00716800 1.10981100 H 3.75684500 4.20923900 0.08536600 C -3.72495600 -1.12199900 -1.03401000 H -3.38355400 -3.06210900 1.92643500 C -5.15593300 -0.02613400 1.10932000 H -1.90148100 -4.37537700 -0.80264700 H -3.22256300 0.43006600 1.95757900 H -4.01307700 -0.29774700 -1.14478000 C -5.12762200 -1.15288100 -1.03929900 H 5.11670400 -3.68260600 -0.07421500 H -3.16598900 -1.54586000 -1.86381900 H 6.71787900 0.31786800 -0.05271400 C -5.84738600 -0.60273800 0.03167500 H 5.22656700 2.24152500 0.01607900 H -5.70573000 0.38872800 1.94811000 H -5.65443100 -1.60498500 -1.87355800 benzoanthra_rad_3Ph: H -6.93219800 -0.62762900 0.03038800 E = -885.03613 H 0.98072500 -2.85268900 0.09842800 rad_freq: E = -1007.4742302

0 2 C -1.29663900 -0.68569900 0.00329500 C -0.65260800 0.58679100 -0.06522400 C 0.78026600 0.68512900 -0.10029900 C -0.79762400 3.05490400 -0.21704600 123 C 0.59666600 3.13317900 -0.29534000 H 2.48597200 3.91593700 0.91909500 C 1.37878000 1.97731400 -0.24300500 C 4.13011400 1.14537200 2.48700400 C -0.48657200 -1.84016900 0.02123400 H 4.83257800 0.30881400 2.57261200 C 0.90934400 -1.74540500 0.00351600 H 3.24066800 0.91669100 3.08496500 C 1.56625700 -0.51003300 -0.03667500 C 5.18657200 0.84769600 -0.83519700 H 2.45611200 2.05231000 -0.33670400 H 4.85814100 0.84535700 -1.88052600 C -2.85136000 1.70202800 -0.06775000 H 6.04938200 1.51761000 -0.74337000 C -2.75696400 -0.76115200 0.04871300 H 0.69840800 2.37762900 -0.02789100 C -4.94260000 0.38735300 0.05845900 H 3.09694500 -1.52605500 1.82395200 C -5.59969500 -0.82828900 0.13230600 H 5.10758600 -3.41103100 -2.31601000 C -3.45846000 -1.99077500 0.12587400 H 2.99924000 -2.09638300 -2.43874800 C -4.84742000 -2.03079100 0.16645000 H 5.21627000 -2.82288300 1.95507400 H -6.68335600 -0.86670400 0.16441700 H 6.23114300 -3.76841300 -0.11838400 C -3.51792500 0.44970000 0.01461400 H 1.17389200 -3.47184000 -0.99633200 H -5.50409200 1.31710700 0.03165200 C -3.23752300 -0.35001100 -1.12020100 H 1.07698400 4.09976500 -0.40577800 C -1.76822700 1.70138900 -0.96802100 C -1.44763200 1.79386300 -0.11308500 C -4.12034300 1.96718100 -1.56161200 H -1.40335000 3.95584000 -0.25181300 C -3.97299300 3.35600400 -1.61375800 H -3.44390700 2.61345700 -0.10049000 C -1.63157900 3.10451700 -1.03778200 H -5.35959200 -2.98536400 0.22601300 C -2.71704500 3.92844000 -1.34776900 H -2.91231400 -2.92631000 0.15604600 H -4.82030700 3.98510500 -1.86655000 H 1.50478100 -2.65212700 0.05720600 H -0.66285500 3.56266200 -0.87014200 C 3.05437100 -0.49366300 0.01282100 C -3.03384600 1.12948200 -1.24053100 C 3.79734400 -1.31744000 -0.85559200 H -1.00200500 -4.42028900 -1.68737300 C 3.74745800 0.28422900 0.96253200 C -1.99712200 -1.18346000 -1.23436400 C 5.19692700 -1.35648600 -0.78542700 H -3.02991800 -2.97912700 -1.78797200 H 3.27341000 -1.91260500 -1.59841600 H 4.60456000 2.04012300 2.90604900 C 5.14601000 0.24410300 1.03631200 H 4.13545300 4.13293900 0.30892700 H 3.18374000 0.89963600 1.65809300 H 5.50297200 -0.17004900 -0.57619900 C 5.87694300 -0.57473900 0.16049100 H -2.58495300 5.00419800 -1.39466800 H 5.75403100 -1.99057900 -1.46760300 H -5.08829200 1.51549100 -1.76848400 H 5.66311200 0.84200000 1.77984700 H -4.01890900 -0.70116200 -1.80468400 H 6.96016500 -0.60480500 0.21708500 Sn -3.99318900 -0.67972200 0.91379000 H -0.93491400 -2.82533600 0.06740100 C -2.48256300 0.07738600 2.20193900 H -1.54114900 -0.46085000 2.04281500 2SnMe3: H -2.30475500 1.13758400 1.98759800 E = -1130.5356944 H -2.77008300 -0.02256300 3.25458200 C -4.29689000 -2.77002800 1.17824100 H -5.03683200 -3.15392700 0.46669400 H -3.35665100 -3.31021000 1.02333900 H -4.65594100 -2.98175200 2.19183600 C -5.82152900 0.39287100 1.12699100 H -6.26237000 0.21062700 2.11376900 H -5.64665500 1.46898900 1.02056400 H -6.54826700 0.08375300 0.36686500

Sn_07: E = -1008.0971956

0 1 C -0.61117600 0.81565100 -0.67464400 C -0.72631200 -0.59820400 -0.91188400 C 0.43312900 -1.43419800 -0.81159600 C -2.06911000 -2.53917100 -1.53134200 C -0.91559000 -3.36156000 -1.46461800 C 0.30504400 -2.83015800 -1.09114100 C 0.61005000 1.31614700 -0.24229000 C 1.77172500 0.50063000 -0.08836300 C 1.68676200 -0.85682000 -0.40126200 Sn 3.60690400 1.47213200 0.44371700 0 1 C 2.91225200 -1.70945600 -0.31818100 C 0.18725600 1.55202900 -0.00547900 C 3.54725700 -1.92603400 0.91893500 C 0.56868600 0.32130600 -0.64836200 C 4.73936900 -2.66435600 0.99284700 C 1.93037200 -0.12866100 -0.59952500 C 5.30828700 -3.20009600 -0.17231700 C -0.02363600 -1.62952200 -1.99210600 C 4.67318600 -3.00054200 -1.41015000 C 1.32627600 -2.06156100 -1.96424800 C 3.48346200 -2.26369800 -1.48050100 C 2.27922000 -1.34374800 -1.26516800 C 3.21309000 3.55415500 0.18226100 C 1.13208200 2.21568300 0.76543500 H 2.82026600 3.75773900 -0.82089000 C 2.46525000 1.74809900 0.85358000 124 C 2.89336000 0.62661000 0.15911600 C -1.55184100 4.10924700 0.14447300 Sn -2.57998000 -1.28717800 0.54990400 C -0.48449300 3.29008600 0.17457400 C 4.33351900 0.24706000 0.22220600 C -0.89029800 -0.96864200 0.05415600 C 4.97238800 0.11446200 1.46987900 C 0.39170300 -0.42333800 0.07169500 C 6.33977200 -0.18716800 1.54828500 C 0.52617500 1.00054300 0.08676000 C 7.09111500 -0.35792400 0.37606200 Sn 2.05757400 -1.76597500 -0.05380800 C 6.46479500 -0.22267600 -0.87367800 C 1.90508000 1.58063700 0.07266400 C 5.09788400 0.07595400 -0.94960000 C 2.78256600 1.35974000 1.15046800 C -1.40631300 -0.64064200 2.19888700 C 4.10235700 1.83594600 1.10826000 H -0.35048600 -0.88335900 2.03336200 C 4.55987800 2.54199500 -0.01487500 H -1.48820500 0.44587400 2.31783300 C 3.68694900 2.77763700 -1.09017800 C -4.64426600 -0.84421100 0.83082700 C 2.36938000 2.30177400 -1.04416900 H -5.23349200 -1.13671700 -0.04582000 C 1.19299200 -3.63685500 -0.60763200 H -4.78019500 0.23025800 0.99536000 H 0.57566000 -4.04074600 0.20375900 C -2.28576500 -3.35361500 0.13058900 H 0.56641700 -3.53320500 -1.50104900 H -1.22266600 -3.56039700 -0.03314100 C 3.43366800 -1.09858000 -1.53039600 H -2.63118700 -3.96788000 0.96999700 H 4.03184700 -0.26614100 -1.14032700 H 0.86852900 3.12102600 1.30031200 H 2.90047800 -0.74592200 -2.42023900 H 4.38810200 0.23321600 2.37821900 C 3.04183400 -2.02308500 1.82279100 H 7.04052100 -0.34244500 -1.78590700 H 3.87523700 -1.31845800 1.91912900 H 4.62144300 0.20115300 -1.91800800 H 2.34596900 -1.85672300 2.65295000 H 6.81405900 -0.29292600 2.51881900 H -0.99627700 -2.04931000 0.03438600 H 8.14935400 -0.59122000 0.43361000 H 2.42376400 0.82548100 2.02676600 H 3.29652500 -1.71146400 -1.19887600 H 4.03365900 3.32258900 -1.96234800 C -1.86795400 -0.12952900 -1.17445300 H 1.69585700 2.46978700 -1.88013300 C -1.16977900 2.10866700 -0.23859100 H 4.76675100 1.65916100 1.94834100 C -3.42891200 1.84888100 -1.12219700 H 5.58127100 2.90656900 -0.05144800 C -3.73667700 3.16919800 -0.78163600 H 0.51160200 3.70442000 0.29114700 C -1.49008800 3.44431100 0.08676100 C -4.33893500 1.52240500 0.00968200 C -2.75784800 3.97251000 -0.17132300 C -3.39899500 -0.76304500 0.01567800 H -4.72095700 3.57272300 -0.99607500 C -5.84052900 -0.45444700 -0.01503800 H -0.73549000 4.08895700 0.52415000 C -6.03252500 -1.82691100 -0.02559400 C -2.15631700 1.30574300 -0.85852400 C -3.62273300 -2.16663100 0.00391900 H 1.60387800 -2.97789300 -2.47520100 C -4.90831600 -2.69021500 -0.01638700 C -0.41699800 -0.47717000 -1.32238000 H -7.03487200 -2.24162000 -0.04157600 H -0.77039500 -2.22569900 -2.51102800 H -2.78363200 -2.85243600 0.01058400 H -5.03945000 -1.37982300 1.70154600 C -4.53121500 0.09774800 0.00498000 H -1.73359000 -1.11891500 3.12901500 H -1.41507300 5.18443800 0.22743800 H -2.83990100 -3.65683300 -0.76502100 C -3.09535600 2.09468800 0.02247200 H -2.97906800 5.00296400 0.08611900 H 4.11081700 -1.90730200 -1.82846200 H -4.17859200 1.22202000 -1.60017300 H 1.97869600 -4.36930200 -0.82636700 H 3.18599700 2.31245200 1.43832200 H 3.43808100 -3.04161900 1.90683800 H -2.45028700 -0.47068700 -2.03876400 H -5.05447100 -3.76523700 -0.02515600 H -6.69214500 0.22040200 -0.02294800 Scheme 7 H -5.22434500 2.15592100 -0.00399000 H -3.59426800 4.04797500 0.77338200 CH2_06: H -3.37076100 3.98504400 -0.96082300 E = -1008.081814 CH2_07: E = -1008.091225

0 1 C -2.06621300 -0.16864400 0.04069500 C -1.91852600 1.24401400 0.04691000 C -0.60737100 1.82327800 0.08501800

C -2.96339400 3.60815200 -0.01083000 0 1 125 C 2.05594400 -0.12760200 0.07993500 C 2.09874300 -0.21913500 0.02099300 C 1.89425800 1.30134600 0.10172700 C 1.93060000 1.18956500 0.05198000 C 0.57711800 1.86636900 0.07153100 C 0.61860700 1.75972400 0.08823600 C 2.84486000 3.54412600 0.15654600 C 2.93444200 3.48988600 0.07346900 C 1.54386500 4.10779900 0.11540900 C 1.71041300 4.05797400 0.14898600 C 0.43246200 3.28710000 0.08523700 C 0.47743000 3.24770400 0.21403600 C 0.91839900 -0.92112700 0.10899400 C 0.93554300 -1.02677600 0.03742800 C -0.40677500 -0.38732600 0.10412900 C -0.35576200 -0.49591400 0.04986900 C -0.57031300 0.99636300 0.05985000 C -0.51295000 0.92338300 0.05758700 Sn -2.03945200 -1.77381800 0.02048800 Sn -2.00546300 -1.87514100 0.00662600 C -1.94884700 1.57147800 -0.01279000 C -1.91374100 1.44525200 -0.02111200 C -2.84629200 1.40733000 1.05821100 C -2.79169800 1.28481800 1.06222400 C -4.16603000 1.87749400 0.96447800 C -4.13006900 1.69565200 0.95843500 C -4.60146400 2.52219200 -0.20302300 C -4.60056200 2.26335900 -0.23423200 C -3.70748600 2.70229400 -1.27222600 C -3.72423200 2.42280500 -1.32142900 C -2.39065400 2.23317300 -1.17505400 C -2.39022400 2.01504100 -1.21482700 C -1.12802000 -3.64420600 -0.45654300 C -1.07911100 -3.74538700 -0.44819300 H -0.51055200 -3.56468200 -1.35897200 H -0.47492200 -3.68042800 -1.36082500 H -0.49417200 -3.99383200 0.36730900 H -0.43421800 -4.07853500 0.37414300 C -3.01914600 -1.97013000 1.90673000 C -2.93061000 -2.04049500 1.92072000 H -3.86862000 -1.28084500 1.96890200 H -3.79007100 -1.36453800 1.98488000 H -2.32932700 -1.74888700 2.72900100 H -2.22592000 -1.78451900 2.71988300 C -3.43801000 -1.21231000 -1.47912800 C -3.43521000 -1.36632600 -1.47697000 H -4.02212700 -0.34595200 -1.14560800 H -4.03480900 -0.51237800 -1.14012700 H -2.92319500 -0.93902600 -2.40681700 H -2.94639900 -1.08848900 -2.41693200 H 1.02783900 -2.00155800 0.12073800 H 1.05024300 -2.10668400 0.02604100 H -2.50313700 0.92100800 1.96785000 H -2.42151400 0.86423900 1.99404600 H -4.03818400 3.19898800 -2.17869900 H -4.08173100 2.86394600 -2.24627600 H -1.70127100 2.35791900 -2.00559600 H -1.70936200 2.14304900 -2.05145200 H -4.84714900 1.74398400 1.79901600 H -4.79712500 1.57990200 1.80696500 H -5.62200600 2.88300300 -0.27916000 H -5.63411300 2.58389100 -0.31555700 H -0.56344400 3.71635400 0.08509000 C 4.36131100 1.48874400 -0.00414700 C 4.42641900 1.60899700 0.31571200 C 3.44025000 -0.79998700 -0.02448200 C 3.42132900 -0.71227000 -0.01698100 C 5.88220900 -0.46720800 -0.08123100 C 5.84276500 -0.43159000 -0.03539000 C 6.08615700 -1.83769500 -0.11391000 C 6.02840900 -1.80215200 -0.23735900 C 3.67681700 -2.19914800 -0.05937600 C 3.62114600 -2.09355400 -0.23577800 C 4.96884500 -2.70854100 -0.10282400 C 4.90356000 -2.63717600 -0.34038600 H 7.09091100 -2.24431100 -0.14860100 H 7.02853500 -2.21398000 -0.32219600 H 2.84602700 -2.89468100 -0.05429300 H 2.77036900 -2.75701500 -0.34107600 C 4.56784000 0.06919300 -0.03628200 C 4.55539000 0.12078500 0.07541000 H 1.56429400 5.13205900 0.19144200 H 1.42546100 5.18632100 0.12311900 C 3.10493800 2.04184600 0.04084800 C 3.02835400 2.17100800 0.16711800 H -3.28088500 -3.06577800 2.08689500 H 3.71180000 4.19872800 0.20065600 H -1.84371000 -4.51523700 -0.60444700 H -3.39304300 -2.99207500 2.03798400 H -4.10538900 -2.21207100 -1.67011100 H -1.89474900 -4.40671700 -0.63616600 H 5.12381700 -3.78194900 -0.12895700 H -4.12723900 -2.03712500 -1.69435100 H 6.72673700 0.21614900 -0.08980700 H 5.02739100 -3.70174400 -0.50942500 H 5.23426200 2.13842600 -0.01632800 H 6.70489600 0.22718600 0.03717500 O -0.62424800 3.81638700 0.39603700 H 4.77857300 1.82593200 1.33512000 H 3.83114400 4.10387500 0.04502100 H 5.10851100 2.14445800 -0.35643900 ket_06_freq: ket_04_freq: E = -1082.076768 E = -1082.069061

0 1 C 1.92537500 -0.47043000 0.04667700 C 1.90150900 0.94739500 0.06137000 0 1 C 0.65571200 1.64530700 0.08776100 126 C 3.14356300 3.17781000 0.07257700 0 1 C 1.82750200 3.83114000 0.14304100 C 1.89879800 -0.32045000 0.04907600 C 0.67873800 3.11096200 0.15074200 C 1.82048400 1.11027400 0.06279400 C 0.68305300 -1.15819000 0.06392100 C 0.54358100 1.75436300 0.08935700 C -0.54805900 -0.49846300 0.08236200 C 2.91476100 3.30287200 0.09595400 C -0.55299100 0.92995600 0.08613400 C 1.65305300 3.93979100 0.14663700 Sn -2.33730800 -1.68056600 -0.03778800 C 0.49446800 3.18085700 0.14519100 C -1.86819300 1.63988200 0.05133800 C 0.71278600 -1.04458800 0.07333900 C -2.77245900 1.51763400 1.12221400 C -0.57760000 -0.43460000 0.08945100 C -4.03137400 2.13530400 1.06661900 C -0.65557900 0.95946900 0.08742500 C -4.39906300 2.88290800 -0.06314600 Sn -2.30340700 -1.70663900 -0.03530200 C -3.49863700 3.01544200 -1.13307100 C -1.99449700 1.62347300 0.05227400 C -2.24132000 2.39914300 -1.07451800 C -2.89232400 1.47750900 1.12535000 C -1.64990800 -3.62527000 -0.58082200 C -4.17575300 2.04313000 1.06429600 H -1.01644100 -3.58580100 -1.47450100 C -4.57316600 2.76416100 -0.07206300 H -1.07553600 -4.08512900 0.23234800 C -3.67781200 2.92411800 -1.14306100 C -3.32863400 -1.81448200 1.84666200 C -2.39683400 2.36027700 -1.07892500 H -4.11164800 -1.05225000 1.92548800 C -1.51685600 -3.60977800 -0.59227900 H -2.61968000 -1.67280700 2.67030300 H -0.87753700 -3.52956200 -1.47915700 C -3.63525800 -0.88649700 -1.52097800 H -0.92758300 -4.04857400 0.22187700 H -4.13140300 0.01621800 -1.14441200 C -3.28460800 -1.90293600 1.84870000 H -3.07106500 -0.61345900 -2.41959000 H -4.08757900 -1.16339900 1.94196800 H 0.68897700 -2.24445000 0.04479200 H -2.57741500 -1.75529300 2.67273200 H -2.48075300 0.95160800 2.00334000 C -3.64037000 -0.96939300 -1.51315400 H -3.77713500 3.59125100 -2.00958500 H -4.18995700 -0.10183200 -1.12814200 H -1.54898600 2.48736000 -1.90735500 H -3.08822700 -0.65263900 -2.40492800 H -4.71757000 2.03792000 1.90178700 H 0.75674200 -2.12998800 0.06318100 H -5.37284400 3.35927800 -0.10890500 H -2.57733200 0.93193500 2.01123800 H -0.27505000 3.62458600 0.22179800 H -3.97941800 3.47965400 -2.02505400 C 4.34364200 1.02283800 0.01251000 H -1.70853300 2.46901100 -1.91269500 C 3.20533800 -1.17167700 0.00807300 H -4.85786300 1.92512400 1.90017100 C 5.66947100 -1.06575100 -0.04912600 H -5.56591600 3.19917300 -0.12276600 C 5.74509200 -2.44864400 -0.07110100 H -0.47226100 3.67014900 0.20096800 C 3.31132700 -2.58781500 -0.01538000 C 4.34642200 1.29033100 0.02476000 C 4.55078200 -3.21288100 -0.05410800 C 3.22766100 -0.97671000 0.00701000 H 6.70719700 -2.94808500 -0.10222600 C 5.67642600 -0.79924300 -0.04830500 H 2.41864900 -3.20227300 -0.00473000 C 5.79708000 -2.18732700 -0.07996700 C 4.40969300 -0.40885300 -0.00967700 C 3.37047500 -2.38119500 -0.02627600 H 1.83001400 4.91449100 0.19718000 C 4.63196600 -2.97805000 -0.06885300 C 3.14328100 1.68729300 0.04760400 H 6.77494800 -2.65475300 -0.11472600 H -3.79369900 -2.80020700 1.96232400 H 2.49614100 -3.02118800 -0.02213000 H -2.50149100 -4.27994300 -0.79923600 C 4.40633000 -0.19440100 -0.00538600 H -4.40291400 -1.61677000 -1.80133100 H 1.59535200 5.02157800 0.19308300 H 4.60707700 -4.29631400 -0.07226800 C 3.00058000 1.91744900 0.06020500 H 6.57195800 -0.46147700 -0.06186200 H 3.83665600 3.87529500 0.09402300 O 4.20856100 3.84151400 0.04611200 H -3.72254300 -2.90261200 1.94885600 H 5.26020000 1.60804700 0.00106100 H -2.33222500 -4.30424900 -0.82515300 H -4.36275000 -1.73942700 -1.80716300 ket_07_freq: H 4.71194000 -4.06005200 -0.09488400 E = -1082.086629 O 5.39029800 1.98482400 0.01860100 H 6.54652600 -0.15139300 -0.05629900

127 Additional Data

DH‡ = +13.8 DH = -13.4 DG‡ = +16.7 2.26 Å DG = -9.9 H OMe OMe

SnMe3 SnMe3

Scheme 42. Additional pyrene isomer vinyl radical attack.

4pyr_Vrad_f: Sn -3.26972200 -0.90651400 0.02328800 E = -1199.263566 C -4.10528900 -2.19653000 -1.44854100 H -3.50655500 -3.11105300 -1.50766200 H -5.13925000 -2.46262000 -1.20092100 H -4.10241700 -1.71226600 -2.43154700 C -4.48869000 0.82655700 0.26279400 H -5.47948600 0.56748300 0.65430200 H -4.01925600 1.53625300 0.95466700 H -4.62067900 1.33752400 -0.69834700 C -3.04333200 -1.88104100 1.90271500 H -4.01387000 -2.21947300 2.28349700 H -2.38497400 -2.74845500 1.78880100 H -2.60638100 -1.19810100 2.64094500 H 1.54984100 -0.65971200 -2.91943800 C 5.13934500 0.12869400 -0.08902500

0 2 C 4.17124600 -0.01043900 -2.74026100 C 1.04404500 -0.87290300 -0.86342400 C 5.99113500 0.39017300 -1.17955700 C 1.51547500 -0.81761000 0.51679000 C 5.51001300 0.32109000 -2.49328500 C 0.67529500 -1.08376800 1.61742900 H 3.80030600 -0.06030100 -3.76001900 C 3.37629700 -0.40958600 2.09795500 H 6.17718600 0.52701500 -3.32352700 C 2.50447400 -0.67622300 3.16979900 H 7.02950200 0.64781800 -0.99073900 C 1.16770000 -1.01197700 2.92752900 H 2.88118100 -0.62140900 4.18735200 C -0.41100300 -1.15083300 -1.18572600 H 0.50334200 -1.22311100 3.75933700 C -1.38531300 -0.09576100 -0.66567800 C 5.60775200 0.19265300 1.27899200 C -1.15334600 1.19045500 -0.60755000 C 4.76507800 -0.06452600 2.32082500 C -1.28618500 2.55342800 -0.32297100 H 5.12041200 -0.01580400 3.34642100 C -0.85543000 3.06625800 0.94194600 H 6.64808700 0.45074300 1.45621600 C -0.97800400 4.42415200 1.23216500 C -1.51987100 5.31545300 0.28436500 4pyr_radIM_RR_6_TS_Vratt_QST3_3: C -1.93898400 4.82590700 -0.96859700 E = -1199.240259 C -1.82495500 3.47106000 -1.27764400 H -0.51125800 -1.21844700 -2.28127100 H -0.42838000 2.37752500 1.66509200 H -2.35623700 5.50965500 -1.70123300 H -2.14884800 3.09448200 -2.24275600 H -0.64912600 4.79686600 2.19710400 H -1.61042400 6.37125200 0.51627800 C 3.77485800 -0.20949300 -0.33380800 C 1.90705000 -0.61918200 -1.89203200 C 3.29341200 -0.27735700 -1.67364500 C 2.88431900 -0.48125200 0.75858200 O -0.90365600 -2.40124500 -0.61290500

C -0.17746800 -3.58282300 -1.02485400 0 2 H -0.71779600 -4.43691900 -0.61485900 C 1.23034700 -1.05133700 0.87961800 H -0.14533800 -3.65449300 -2.12072600 C 1.65343400 0.32588900 0.96382600 H 0.84607300 -3.56817800 -0.63257800 C 0.81634800 1.31332600 1.56730600 H -0.35804500 -1.35808600 1.44275600 C 3.23429100 2.09323000 0.26864400

128 C 2.36464700 3.06091600 0.83251600 0 2 C 1.19738700 2.68186400 1.48522200 C 1.37803300 -1.07161600 0.41656200 C -0.20051800 -1.38699100 1.24574100 C 1.65981400 0.30066800 0.57054000 C -1.18177300 -0.51778300 0.44329400 C 0.55749100 1.19907400 1.09308800 C -1.05749000 0.80056400 0.40179300 C 3.21318400 2.20957800 0.29950800 C -1.77117400 1.98471000 0.01145400 C 2.13611800 3.11159200 0.67796900 C -3.02074800 2.28131300 0.61406600 C 0.89856300 2.66611600 1.00513500 C -3.72021800 3.44002400 0.25942100 C -0.01929800 -1.53625500 0.77108300 C -3.18594100 4.32534900 -0.69310200 C -1.07536800 -0.53889600 0.31484500 C -1.93752300 4.04917100 -1.27944100 C -0.80456600 0.77569800 0.49528800 C -1.22729300 2.89699400 -0.92514300 C -1.83259500 1.82069200 0.21604300 H -0.36871500 -2.45425200 1.02680700 C -3.03008700 1.82958900 0.95661600 H -3.42115000 1.59664200 1.35723300 C -4.04185900 2.75919000 0.67053000 H -1.51974200 4.73539900 -2.00910900 C -3.86433700 3.69303700 -0.36109200 H -0.25723800 2.68423300 -1.36510700 C -2.66550900 3.70011700 -1.09541400 H -4.67901100 3.65337400 0.72123000 C -1.65414900 2.77489000 -0.80489700 H -3.73105600 5.22200900 -0.96912700 H -0.18813100 -2.53497200 0.33859300 C 3.72413700 -0.27925200 -0.25091900 H -3.15734200 1.10878900 1.76051100 C 2.04670400 -1.99777700 0.31302600 H -2.52444900 4.42011800 -1.89501900 C 3.33616100 -1.65387400 -0.23408800 H -0.73222700 2.77291000 -1.37980000 C 2.86559000 0.71363800 0.32728200 H -4.96017000 2.75366200 1.24906300 O -0.51163100 -1.16428800 2.65463100 H -4.64675800 4.40968500 -0.58892800 C 0.31227200 -1.94889300 3.55277600 C 3.95070300 -0.09550800 -0.23232900 H -0.09383000 -1.79694900 4.55316800 C 2.35188400 -1.95077200 -0.04513300 H 0.26550500 -3.01629900 3.29305800 C 3.66277200 -1.49023800 -0.36553200 H 1.35783000 -1.61918200 3.51904000 C 2.93529100 0.80330100 0.22555600 H 0.09589800 1.00439500 2.31846200 O -0.19375100 -1.64137700 2.22654700 Sn -2.81096200 -1.44404900 -0.60529200 C 0.66791000 -2.62694600 2.84688300 C -2.09679300 -3.34941800 -1.24796300 H 0.35553100 -2.69434400 3.88964600 H -2.04201800 -4.05022300 -0.40697800 H 0.55000800 -3.60770300 2.36302800 H -2.76404500 -3.77865400 -2.00401700 H 1.72146400 -2.32676700 2.79377900 H -1.09715000 -3.25457900 -1.68784600 H 0.43829700 0.96411300 2.16953800 C -3.33612100 -0.19968000 -2.24457200 Sn -2.89582800 -1.28346300 -0.51995500 H -4.06769300 -0.69152500 -2.89562500 C -2.41183300 -3.24569700 -1.20992700 H -3.76587200 0.74190700 -1.88435600 H -2.21281900 -3.91851200 -0.36708900 H -2.44774000 0.04187200 -2.83856100 H -3.24366700 -3.66579100 -1.78726000 C -4.44531600 -1.69653400 0.73829800 H -1.52593400 -3.22856600 -1.85581200 H -4.95063700 -0.73932700 0.90867200 C -3.52269700 -0.05097200 -2.13627700 H -5.17825000 -2.40775400 0.34099100 H -4.30033100 -0.54658900 -2.72891600 H -4.08326600 -2.06919200 1.70278300 H -3.92150400 0.89818600 -1.75759300 H 1.71106800 -3.03073800 0.23642900 H -2.67523100 0.17527700 -2.79301400 C 4.96277800 0.10372500 -0.84931600 C -4.42643000 -1.44221000 0.95707900 C 4.20025600 -2.62121400 -0.78733600 H -5.08032700 -2.29645100 0.74754700 C 5.80221400 -0.89198300 -1.38956700 H -3.97785600 -1.58310200 1.94702600 C 5.42384200 -2.24093500 -1.35302100 H -5.03932700 -0.53392500 0.97593000 H 3.90563100 -3.66692500 -0.77428300 H 2.11930100 -3.00746300 -0.16376100 H 6.08180900 -2.99523100 -1.77174000 C 5.25238500 0.40202500 -0.56504500 H 6.74865100 -0.60190500 -1.83708300 C 4.68683700 -2.36785800 -0.81810500 H 2.64286400 4.11034000 0.77941400 C 6.24392500 -0.50716400 -1.00742000 H 0.56643500 3.43211400 1.95088100 C 5.95645300 -1.87578400 -1.12954500 C 5.31543600 1.50511700 -0.88163800 H 4.46827400 -3.42696900 -0.91955200 C 4.48197900 2.45508400 -0.35286000 H 6.72844000 -2.55686300 -1.47238200 H 4.75315200 3.50695800 -0.38776100 H 7.23260700 -0.13210200 -1.25570800 H 6.25820900 1.78881000 -1.34093200 H 2.34853900 4.17789800 0.68220100 H 0.11934000 3.37081300 1.28180600 4pyr_radIM_RR_6: C 5.50390900 1.80668400 -0.44406400 HF -1199.288203 C 4.50183700 2.67855900 -0.03312000 H 4.70343800 3.74440900 0.03152600 H 6.49191800 2.18306600 -0.69290500

129 Additional Computational Work

Scheme 43. Hydrogen abstraction where X = SnMe3.

Scheme 44. Hydrogen abstraction where X = H.

130

Scheme 45. Relative stabilities of intermediates.

benzoanthra_6H_3Ph: H 5.71654900 -2.08035500 -1.44368800 E = -885.6435714 H 5.68389500 0.88276700 1.68627300 H 6.95253500 -0.63023600 0.16344000 H -0.94008700 -2.85456800 0.15076900

benzoanthra_7H_3Ph: E = -885.6530066

0 1 C -1.29578800 -0.70868200 0.03520400 C -0.65154000 0.55756800 -0.04008800 C 0.78030600 0.63957300 -0.09276000 C -0.79114400 3.13754400 -0.08433200 C 0.69224400 3.09976500 -0.34164700 C 1.40225000 1.95669700 -0.32208200 C -0.48401500 -1.87403300 0.08588700 C 0.89543200 -1.78145000 0.07406200

C 1.55355900 -0.52657300 -0.00882100 0 1 H 2.46878400 1.97899200 -0.51875200 C -1.27508900 -0.68298400 -0.08249500 C -2.81788100 1.67787900 -0.07292200 C -0.62763300 0.59951200 0.02637300 C -2.75200600 -0.78815000 0.05591700 C 0.80407600 0.67999700 0.09939100 C -4.92445500 0.36596300 0.00321200 C -0.76189800 3.02244800 0.26864600 C -5.59113100 -0.84692500 0.07400500 C 0.64710000 3.09765000 0.40766200 C -3.45883800 -2.01884700 0.12974900 C 1.41446100 1.95255600 0.31634000 C -4.84666500 -2.05154400 0.13833700 C -0.48085100 -1.81763700 -0.15858700 H -6.67546900 -0.87903400 0.08088300 C 0.93247600 -1.73563200 -0.13201300 C -3.50449300 0.41655300 -0.00663200 C 1.58915900 -0.52230300 -0.00915500 H -5.48077800 1.29806000 -0.04536300 H 2.49081400 2.00848300 0.43211200 H 1.18829500 4.04649200 -0.53813200 C -2.89703200 1.78114800 -0.12230800 C -1.45241600 1.76977100 -0.07865000 C -2.76058800 -0.76580400 -0.07043900 H -0.96837800 3.62527300 0.88655100 C -4.93904300 0.32779600 -0.05130300 H -3.41941600 2.58464300 -0.10747400 C -5.59118400 -0.90788400 -0.02602100 H -5.36529700 -3.00288800 0.19489000 C -3.43093000 -2.00874600 -0.03301100 H -2.91673500 -2.95586100 0.17986800 C -4.82506900 -2.08560800 -0.01478400 H 1.49869200 -2.68140600 0.14895100 H -6.67483500 -0.95655700 -0.00897300 H -1.27887000 3.77894100 -0.82948300 C -3.53660000 0.41131900 -0.07389000 C 3.04440700 -0.51861800 0.01867000 H -5.51980800 1.24704000 -0.05393000 C 3.77119100 -1.37909900 -0.82686600 H 1.11941500 4.05824200 0.58475900 C 3.75380000 0.29402700 0.92519000 C -1.39667700 1.80629100 0.07794200 C 5.17171600 -1.41778000 -0.77882200 H -1.35502700 3.93240800 0.31419300 H 3.23457600 -2.00454500 -1.53518100 H -3.12127800 2.23226900 -1.10030500 C 5.15359800 0.25511700 0.97731600 H -5.31299000 -3.05422900 0.01462800 H 3.20140200 0.94063400 1.60151100 H -2.86418600 -2.93200600 -0.00757700 C 5.86858300 -0.59990800 0.12356200 H 1.51716000 -2.64508600 -0.23522700

131 C 3.07994400 -0.50513200 -0.02259600 H 2.82701400 -2.67835200 -0.53594900 C 3.79371000 0.29760500 -0.93517200 C 4.54754700 0.22878400 0.14265300 C 3.80241200 -1.35064800 0.84088200 H 1.41996500 5.18746500 0.13117400 C 5.19352400 0.25906300 -0.97838600 C 3.01277500 2.16651100 0.09878700 H 3.24576100 0.93385600 -1.62460500 H 3.70898900 4.19474000 0.14386900 C 5.20368800 -1.38886600 0.80125300 H 5.19076400 2.24881400 0.24115400 H 3.26026300 -1.96530700 1.55409600 H -3.38933600 -3.01702600 2.03425900 C 5.90464400 -0.58303200 -0.10819700 H -1.90375700 -4.40890600 -0.65435800 H 5.72751900 0.87722500 -1.69289300 H -4.14297200 -2.03617300 -1.69306200 H 5.74517400 -2.04117700 1.47889900 H 5.12454000 -3.55118600 -0.81624100 H 6.98888800 -0.61161700 -0.14067300 H 6.68013200 0.30363400 -0.15915100 H -0.92740200 -2.79978300 -0.25779300 H 6.19190800 -0.35999600 1.38648600 H -3.37508400 2.42958300 0.62249700 benzoanthra_8H_3Ph: CH2_08_freq: E = -885.6145043 E = -1008.0526697

0 1 C -1.24608800 -0.69924700 0.06400400 C -0.60302400 0.57659300 -0.06253200 0 1 C 0.82488900 0.67429200 -0.11489800 C 2.03861500 -0.11903100 0.05081300 C -0.77752100 3.00475800 -0.31874800 C 1.86676500 1.30222200 0.06472300 C 0.63286000 3.09390100 -0.43382800 C 0.55379200 1.86845000 0.06260800 C 1.41726400 1.96020900 -0.33168400 C 2.83825600 3.54569300 0.11330100 C -0.44309700 -1.83344400 0.17221500 C 1.53642500 4.10895200 0.10770000 C 0.96410500 -1.73959000 0.14436700 C 0.41923000 3.29417200 0.08963200 C 1.61529700 -0.51784400 0.01040900 C 0.90012600 -0.92192100 0.10226100 H 2.49361600 2.03373400 -0.43785300 C -0.42027700 -0.39089200 0.09903600 C -2.84455700 1.66960200 -0.01193800 C -0.58829000 0.99813500 0.05972100 C -2.72621200 -0.77864200 0.06845300 Sn -2.05132000 -1.78026500 0.01832400 C -4.98702500 0.42932900 0.37102600 C -1.96894400 1.56846400 0.00209700 C -5.62190800 -0.90085300 0.04692200 C -2.86134900 1.38554600 1.07445000 C -3.41021000 -1.95709700 -0.06445600 C -4.18310800 1.85192600 0.99298800 C -4.86930700 -2.00976100 -0.13073000 C -4.62607600 2.51133200 -0.16348400 H -6.70636200 -0.94885000 0.00217400 C -3.73714600 2.71080200 -1.23340000 C -3.48736700 0.48274500 0.12878600 C -2.41797200 2.24582700 -1.14837500 H -5.48267300 1.23481600 -0.18411200 C -1.13788700 -3.64615200 -0.47207200 H 1.09657300 4.05997200 -0.60383700 H -0.52327400 -3.55932600 -1.37576600 C -1.39594400 1.77227500 -0.14388200 H -0.50079800 -3.99978700 0.34746000 H -1.38408500 3.90427900 -0.37535100 C -3.02599700 -1.99093900 1.90564300 H -5.33929300 -2.96732100 -0.33180400 H -3.88231900 -1.31050700 1.97137100 H -2.87331500 -2.89286400 -0.17899000 H -2.33718000 -1.76548300 2.72761500 H 1.55779100 -2.64095200 0.26599100 C -3.45232300 -1.21284000 -1.47674800 H -3.41278800 2.59812000 -0.01468500 H -4.03483300 -0.34655500 -1.14036400 H -5.17924200 0.64291200 1.43573100 H -2.93851400 -0.93804100 -2.40457800 C 3.10523800 -0.49277600 0.03505600 H 1.02205200 -2.00170100 0.14088600 C 3.83768200 -1.35033000 -0.80838700 H -2.51255400 0.88839300 1.97604800 C 3.80898000 0.32996000 0.93754800 H -4.07329500 3.21954800 -2.13114000 C 5.23867700 -1.37988700 -0.75985600 H -1.73240000 2.38570600 -1.97964100 H 3.30337500 -1.98083800 -1.51370700 H -4.86002400 1.70397800 1.82853000 C 5.20877600 0.29961400 0.98989600 H -5.64845000 2.86880700 -0.23026700 H 3.25332800 0.97470000 1.61279600 H -0.57384200 3.72968500 0.11112400 C 5.92969900 -0.55408100 0.13931200 C 4.34288900 1.57057300 0.16168200 H 5.78798100 -2.04121400 -1.42229000 C 3.40488200 -0.68913900 -0.02557500 H 5.73495900 0.93320300 1.69666700 C 5.94084500 -0.35486400 0.31249100 H 7.01385000 -0.57620900 0.17896700 C 6.08858500 -1.76649900 -0.20141800 H -0.89095900 -2.81184300 0.30796800 C 3.64981300 -2.00040900 -0.33265300 C 5.00566300 -2.52759300 -0.47533200 CH2_10_freq: H 7.09311900 -2.16710800 -0.30482500 132 E = -1008.056723

0 1 0 1 C 1.25293900 -0.68052200 -0.00576700 C 2.04512100 -0.09589600 0.04150000 C 0.59958700 0.59643700 -0.06713200 C 1.85941500 1.32519400 0.06030300 C -0.83022900 0.68542900 -0.09594400 C 0.54030300 1.87877700 0.08052700 C 0.74611600 3.03843200 -0.21222100 C 2.80194500 3.58478300 0.10803200 C -0.66733800 3.12184400 -0.27872800 C 1.49407100 4.13217300 0.14456300 C -1.43824300 1.97625500 -0.22441400 C 0.38862700 3.30271800 0.13318200 C 0.45713500 -1.82281800 -0.00174500 C 0.91173500 -0.90465000 0.06580100 C -0.95166400 -1.73956000 -0.01400900 C -0.41407900 -0.38639800 0.07881300 C -1.61216800 -0.51744700 -0.04035000 C -0.59480300 1.00035600 0.07530400 H -2.51735300 2.04484900 -0.30315600 Sn -2.03370600 -1.78656100 -0.02733300 C 2.83093600 1.71212500 -0.08117500 C -1.98136800 1.55903500 0.04218400 C 2.74073600 -0.75183200 0.04607200 C -2.86135900 1.34865700 1.11974200 C 4.95191800 0.46794500 0.03514500 C -4.18856400 1.80275700 1.05877400 C 5.62931400 -0.69330600 0.12265500 C -4.64944000 2.47710800 -0.08191000 C 3.42775500 -1.92009300 0.14224600 C -3.77296400 2.70412100 -1.15664700 C 4.93038000 -2.02608100 0.18954100 C -2.44846900 2.25115400 -1.09216300 H 6.71577100 -0.69589700 0.14854500 C -1.10891900 -3.63453900 -0.56388000 C 3.48652000 0.52425900 -0.00399800 H -0.49545000 -3.52287200 -1.46553000 H -1.14306000 4.09133000 -0.38332900 H -0.46959100 -4.00404800 0.24694100 C 1.37906900 1.80507300 -0.11769400 C -2.99672700 -2.05284300 1.85885300 H 1.34518500 3.94388600 -0.25088600 H -3.85140900 -1.37339800 1.95083700 H 5.27778700 -2.66856500 -0.63512600 H -2.30241900 -1.85367000 2.68299500 H 2.89397700 -2.86496800 0.19314600 C -3.44881100 -1.19680800 -1.49995900 H -1.53685700 -2.65338700 0.03236700 H -4.04033700 -0.34765600 -1.13680000 H 3.39769200 2.64034400 -0.11773700 H -2.94355500 -0.88972800 -2.42234100 H 5.48485500 1.41465900 -0.00978000 H 1.03472700 -1.98439900 0.06092400 H 5.23133500 -2.55671900 1.10670400 H -2.49898500 0.83996600 2.00947700 C -3.10163000 -0.50404300 0.01158400 H -4.12281200 3.22461600 -2.04235100 C -3.84643900 -1.30060600 -0.87928700 H -1.77242200 2.41242400 -1.92738900 C -3.79122500 0.24589800 0.98558900 H -4.85573700 1.63344200 1.89813900 C -5.24616100 -1.34229200 -0.80571900 H -5.67607800 2.82494100 -0.13271100 H -3.32392500 -1.87242100 -1.64115300 H -0.60959600 3.72412100 0.17951500 C -5.18958600 0.20384700 1.06240900 C 4.33194400 1.63654800 0.05305900 H -3.22508400 0.84220400 1.69568100 C 3.42475700 -0.66124500 -0.00378300 C -5.92312700 -0.58907200 0.16510000 C 5.91622900 -0.24595600 -0.00875200 H -5.80536100 -1.95583700 -1.50478700 C 6.16910700 -1.56797200 -0.06700000 H -5.70450100 0.78012500 1.82439100 C 3.68473200 -1.99314700 -0.07130100 H -7.00624300 -0.62059300 0.22382500 C 5.06659200 -2.59346300 -0.11350000 H 0.90821300 -2.80824400 0.02834400 H 7.19305000 -1.93179800 -0.08466300 C 4.55301400 0.29585500 0.01687500 CH_11a_freq: H 6.73370600 0.47053800 0.02021800 E = -1008.0410387 H 1.36453900 5.20849900 0.18856600 C 2.99383300 2.20890300 0.07150700 H 3.66573200 4.24360800 0.11809000 H 5.17653300 2.32258600 0.06641000 H -3.36092900 -3.08191600 1.95798000 H -1.87075600 -4.39704900 -0.76352300 H -4.13007800 -2.02268600 -1.73540100 H 5.18348200 -3.30258200 0.72122700 H 5.17063700 -3.20778200 -1.02211100 H 2.86753500 -2.70845100 -0.10261700 benzoanthra_10H_3Ph: E = -1008.0567228 133

0 1 C 1.26316300 -0.70050500 0.26366400 0 1 C 0.63244600 0.58182300 0.18251700 C 2.04595200 -0.13779300 0.24362000 C -0.79517400 0.68355800 0.12912800 C 1.89496100 1.28163200 0.17009500 C 0.80472800 3.02451800 0.15538100 C 0.58699100 1.85734500 0.10566200 C -0.60996900 3.12415300 0.15987100 C 2.88220700 3.52061900 0.14640400 C -1.39229900 1.98475900 0.14172700 C 1.58380000 4.09224800 0.12306500 C 0.46600700 -1.83399000 0.29667900 C 0.46249300 3.28393100 0.09835000 C -0.94559000 -1.74074900 0.22017900 C 0.90838300 -0.93015400 0.24220300 C -1.58787100 -0.51558900 0.12036100 C -0.41172200 -0.38971400 0.15992000 H -2.47310500 2.06863100 0.16355200 C -0.56414400 0.99620700 0.08853300 C 2.88192600 1.67452600 0.12294300 Sn -2.04931800 -1.76558000 0.01490800 C 2.77761900 -0.81517700 0.40719900 C -1.93726000 1.57936600 -0.01541900 C 4.97606200 0.37445300 -0.01867200 C -2.86034600 1.41330800 1.03357800 C 5.54743700 -0.80536500 -0.37798100 C -4.17434500 1.89319700 0.91407100 C 3.39403100 -1.97750000 -0.35881100 C -4.57872400 2.55006700 -0.25790500 C 4.70848900 -1.97626900 -0.66965700 C -3.65965000 2.73165800 -1.30528500 H 6.61959400 -0.87586100 -0.53174900 C -2.34848700 2.25246600 -1.18232500 C 3.52657000 0.48286100 0.14857700 C -1.13249000 -3.63613400 -0.45178300 H -1.07815100 4.10267800 0.18043200 H -0.46217300 -3.54174600 -1.31421100 C 1.42701400 1.78359800 0.17042900 H -0.55146200 -4.01321100 0.39846000 H 1.41098300 3.92607500 0.14588800 C -3.08928100 -1.97381300 1.86720500 H 5.15929100 -2.82721600 -1.17063000 H -3.93835600 -1.28248400 1.90800600 H 2.76475500 -2.82589300 -0.60796600 H -2.42533400 -1.76057400 2.71263300 H -1.53881800 -2.65050300 0.21082500 C -3.39014400 -1.17604100 -1.52581100 H 3.45229500 2.59636600 0.02280000 H -3.99234400 -0.32061900 -1.19618200 H 5.57392300 1.27654000 0.08463000 H -2.83785700 -0.87722400 -2.42366900 H 2.96924600 -1.03855300 1.47628900 H 1.01928100 -2.01032800 0.31562400 C -3.07298200 -0.48575800 -0.01090500 H -2.54097400 0.91818100 1.94719500 C -3.88066800 -1.18162900 0.90820700 H -3.96646900 3.23790000 -2.21483200 C -3.69271700 0.18184200 -1.08651500 H -1.64012000 2.37852500 -1.99654300 C -5.27553400 -1.20523600 0.76238600 H -4.87494700 1.75841100 1.73209900 H -3.41085000 -1.69027600 1.74550500 H -5.59452100 2.91932000 -0.35410400 C -5.08554100 0.15694200 -1.23596900 H -0.52780800 3.72617800 0.09034100 H -3.07644500 0.70054000 -1.81558600 C 4.38052700 1.54397300 0.14242400 C -5.88296200 -0.53510100 -0.31020500 C 3.42880400 -0.76203400 0.41118800 H -5.88423300 -1.74101100 1.48365200 C 5.90799400 -0.39097300 0.02550600 H -5.54707200 0.66860200 -2.07445600 C 6.05109100 -1.69591000 -0.32717800 H -6.96186600 -0.55307700 -0.42514300 C 3.62746900 -2.06780500 -0.34623700 H 0.91535500 -2.81802900 0.38876500 C 4.86964700 -2.51395200 -0.63440700 H 7.03813500 -2.12664000 -0.46324400 rad_OMe_6CH2_Sn: C 4.57920100 0.20360200 0.17062700 E = -1123.096335 H 6.77485500 0.25484700 0.14148300 H 1.47398600 5.17169400 0.12453200 C 3.04903600 2.14237200 0.17105900 H 3.75725700 4.16468400 0.14531100 H 5.23303100 2.21541900 0.05523600 H -3.46998200 -2.99552600 1.97888000 H -1.89522700 -4.38499700 -0.69484700 H -4.06472600 -1.99855200 -1.79031400 H 5.01270200 -3.47045600 -1.12736100 H 2.75278800 -2.65601800 -0.60584900 H 3.51438200 -1.03383700 1.48298700 benzoanthra_11aH_3Ph: E = -885.6026589

0 2 134 C 2.01477100 0.03161400 -0.00357400 C 1.80471300 1.41165600 0.14485300 C 0.45335200 1.95306400 0.19864400 C 2.74275000 3.79985300 0.42447500 C 1.30901800 4.23503800 0.53099200 C 0.26741900 3.36509800 0.40726300 C 0.83678500 -0.91099000 0.13409400 C -0.52125300 -0.28816600 -0.09336600 C -0.67364200 1.07495800 -0.00164600 Sn -2.11118500 -1.71094000 -0.15095000 C -2.05191600 1.65633100 -0.09911600 C -2.46579500 2.33179900 -1.26181100 C -3.77756400 2.81360600 -1.37588600 C -4.68918900 2.63202700 -0.32226800

C -4.27888100 1.97298100 0.84682700 0 2 C -2.96531900 1.48926900 0.95720300 C 1.22112500 -0.40325600 -0.09973200 C -1.15420500 -3.53589900 -0.70727200 C 0.52263800 0.77997400 0.19034500 H -0.66120300 -3.44949400 -1.68287500 C -0.93143300 0.77772500 0.30165400 H -0.40065200 -3.79623700 0.04656700 C 0.52715100 3.30240400 0.73084400 C -3.00002500 -1.95537000 1.77042900 C -0.94238600 3.13697600 0.99352200 H -3.85419700 -1.28094400 1.89703900 C -1.60024900 1.96576300 0.76125700 H -2.25061500 -1.73561500 2.53861600 C 0.46934400 -1.71820200 -0.02863700 C -3.58969800 -1.16576700 -1.58350600 C -0.99404300 -1.57416600 -0.31477700 H -4.12087000 -0.26491300 -1.25181100 C -1.66656300 -0.40689200 -0.08108600 H -3.13058400 -0.95188100 -2.55523700 C -3.14822500 -0.37013400 -0.26279100 H 0.96763100 -1.77683300 -0.53205700 C -3.75591200 0.61364400 -1.06765900 H -1.75975200 2.46092200 -2.07739600 C -5.14177800 0.61233400 -1.27287600 H -4.97584700 1.83609700 1.66752700 C -5.94250600 -0.37339500 -0.67336900 H -2.63928000 0.98551800 1.86358200 C -5.34604800 -1.35710100 0.12966500 H -4.09012400 3.32183800 -2.28243500 C -3.95793400 -1.35483300 0.33255000 H -5.70543200 3.00192800 -0.41190400 H 0.90991800 -2.46324400 -0.70385700 H -0.74978700 3.73910400 0.47183600 H -3.13592000 1.36860500 -1.54361900 C 4.20060000 1.81691300 -0.00531700 H -5.95866600 -2.11938700 0.60032900 C 3.33346000 -0.47413900 -0.26628100 H -3.49472200 -2.10486200 0.96744200 C 5.75858400 -0.04097200 -0.51557800 H -5.59474600 1.37198000 -1.90191200 C 5.98957100 -1.37414200 -0.79287600 H -7.01623500 -0.37399100 -0.83061100 C 3.60930700 -1.84859200 -0.56597800 H -2.66972600 1.91196800 0.93857800 C 4.89467600 -2.28421300 -0.82717000 C 2.59765800 2.04902300 0.10760600 H 6.99462200 -1.73082000 -0.99159100 C 2.62682400 -0.36551000 -0.38288700 H 2.79896600 -2.56685700 -0.60764200 C 4.71692000 0.94907000 -0.55814100 C 4.43907800 0.43628600 -0.26107900 C 5.41721100 -0.17815200 -0.94030900 H 1.11867000 5.29036300 0.70555400 C 3.38483200 -1.51489800 -0.78205200 C 2.93021500 2.31284700 0.18075300 C 4.73591900 -1.42373600 -1.05794200 H -3.34816600 -2.98577000 1.90651600 H 6.47909700 -0.12204300 -1.15493200 H -1.87796100 -4.35695900 -0.76362000 H 2.89576200 -2.47635700 -0.88687200 H -4.32034500 -1.97258800 -1.71457600 C 3.31946700 0.88429600 -0.28011300 H 5.07429300 -3.32826900 -1.06220500 H -1.48551900 4.00205500 1.36370400 H 6.58063100 0.66941800 -0.49576600 C 1.23961100 2.02170900 0.33431300 H 5.05310300 2.49358100 0.02152500 H 5.28562800 -2.30676800 -1.36730800 H 3.23544200 4.36546800 -0.38030100 H 5.22046300 1.90782400 -0.46793700 H 3.27696400 4.08307000 1.34430400 H 3.14291900 2.98543200 0.21296500 O 0.68998600 -1.44392500 1.51288000 H 0.66923200 4.05718700 -0.05806400 C 1.73019600 -2.33249400 1.98881200 H 1.01310000 3.72353600 1.62303300 H 1.80871500 -3.22795800 1.35600500 O 0.50353400 -2.27819000 1.34092700 H 2.70370500 -1.83157500 2.02974700 C 1.79741900 -2.73457400 1.80383200 H 1.42937900 -2.62775600 2.99529900 H 2.20652100 -3.50830800 1.13848400 H 2.51607000 -1.91029000 1.88087400 rad_OMe_6CH2_H: H 1.62556300 -3.16277500 2.79244800 E = -1000.653514 H -1.53128400 -2.46344200 -0.62947500

rad_OMe_7CH2_Sn: E = -1123.104177

135 H 2.71397900 -1.89205400 1.98189600 H 1.46160200 -2.82637400 2.85024900

rad_OMe_7CH2_H: E = -1000.660884

0 2 C 2.00213000 0.03941400 0.05042500 C 1.78377900 1.45327100 0.20519200

C 0.45953100 1.99208100 0.14421700 0 2 C 2.66872800 3.71569400 0.46185400 C -1.19305600 -0.40774800 0.02541500 C 1.36616500 4.23991800 0.41581700 C -0.48973100 0.81837700 -0.25044500 C 0.27207700 3.37913100 0.25999400 C 0.94213000 0.84483500 -0.27368200 C 0.82783300 -0.89979800 0.14608600 C -0.52004200 3.20868000 -0.75306800 C -0.53279800 -0.27080900 -0.05961900 C 0.88158400 3.22058500 -0.82328300 C -0.68707000 1.07765200 -0.03819100 C 1.60296900 2.04338700 -0.58297400 Sn -2.11747800 -1.70418400 -0.09210800 C -0.44125400 -1.70874900 -0.10135300 C -2.05997000 1.66540500 -0.15467300 C 1.03197400 -1.56939700 0.14556300 C -2.97067200 1.53915000 0.90977100 C 1.68851900 -0.39263300 0.03895400 C -4.28042700 2.03078200 0.78965000 C 3.16517500 -0.35171600 0.25450500 C -4.68930600 2.65761800 -0.39727800 C 4.00344300 -1.24278400 -0.44021900 C -3.78006500 2.79892100 -1.45930600 C 5.38746300 -1.24862700 -0.21026600 C -2.47195000 2.31003900 -1.33544900 C 5.95058300 -0.36207400 0.71971100 C -1.16855400 -3.52932300 -0.66223600 C 5.12091700 0.53012200 1.41871500 H -0.70316100 -3.44540000 -1.65172000 C 3.73951600 0.53644400 1.18584400 H -0.39476100 -3.78525600 0.07190900 H -0.85278200 -2.47108400 0.57344700 C -2.97836400 -1.92410800 1.84312100 H 3.56541400 -1.91707100 -1.17061000 H -3.81414700 -1.22950100 1.98249900 H 5.54814300 1.21403300 2.14520900 H -2.20941500 -1.71777400 2.59542500 H 3.09814300 1.21785700 1.73803400 C -3.60922800 -1.17761300 -1.51845500 H 6.02240700 -1.93710900 -0.75862100 H -4.14470900 -0.27711600 -1.19330000 H 7.02105300 -0.36467100 0.89774700 H -3.15667900 -0.96998400 -2.49478500 H 2.68592600 2.05738700 -0.63840900 H 0.95386600 -1.73238100 -0.56269700 C -2.71915100 2.00998700 -0.49759600 H -2.64590700 1.05836900 1.82917900 C -2.59957000 -0.37261800 0.39072000 H -4.09210900 3.28145700 -2.37997200 C -4.68682300 0.88784800 0.60069000 H -1.76874200 2.40889900 -2.15774400 C -5.32546600 -0.21770600 1.17888500 H -4.97544100 1.92452000 1.61651100 C -3.26647500 -1.48688400 0.97015400 H -5.70253100 3.03376100 -0.49465300 C -4.60410500 -1.41083900 1.35928800 H -0.73351500 3.78489800 0.22470700 H -6.36420000 -0.15298300 1.48491800 C 4.27985100 1.77544900 0.50511600 H -2.73112600 -2.41380700 1.14016300 C 3.33461700 -0.44976300 -0.27740700 C -3.34608200 0.82552600 0.20195800 C 5.73640600 -0.02459800 -0.48971300 H 1.40748500 4.13955400 -1.05883100 C 5.94437900 -1.31152400 -1.00573900 C -1.20798200 2.02391100 -0.47808200 C 3.56600100 -1.75278400 -0.79749600 H -1.08093400 4.12282500 -0.92934100 C 4.84642200 -2.17600800 -1.15604300 H -5.08456800 -2.27396100 1.80811500 H 6.94063500 -1.63423800 -1.28854800 H -5.23849600 1.81241600 0.45031000 H 2.73805200 -2.43665900 -0.94442600 H -3.04798100 1.99850900 -1.54965000 C 4.45803900 0.41173800 -0.12260500 H -3.10648200 2.94391600 -0.07329000 H 1.20736500 5.30989900 0.49831400 O -0.54101100 -2.24862600 -1.47662100 C 2.88512100 2.33954500 0.36616700 C -1.86576600 -2.68996400 -1.86261400 H 3.51838000 4.38264700 0.58173900 H -2.25664500 -3.43462500 -1.15425300 H -3.34802600 -2.94518200 1.99124000 H -2.57152700 -1.85294000 -1.92326000 H -1.89192900 -4.35199400 -0.69698400 H -1.75462000 -3.14694900 -2.84688900 H -4.33510300 -1.99052800 -1.63864200 H 1.57625700 -2.48006800 0.37726200 H 4.99035000 -3.17314200 -1.55902400 H 6.57913300 0.65083400 -0.36601100 rad_OMe_8CH2_Sn: H 4.50840100 1.68922500 1.58032100 E = -1123.087727 H 5.01392400 2.47871900 0.09564400 O 0.69239600 -1.51394700 1.49236700 C 1.75669200 -2.41627500 1.88320200 H 1.86900000 -3.23411800 1.15692100

136 H 1.83562900 -3.20622100 1.27258100 H 2.72088400 -1.81983400 1.97758100 H 1.45281600 -2.64597700 2.92624900

rad_OMe_8CH2_H: E = -1000.645209

0 2 C 2.00201200 0.07966600 -0.02448300 C 1.75712100 1.47454900 0.13616100 C 0.41727100 1.99771900 0.17962000 C 2.61546100 3.77320200 0.40347300 0 2 C 1.32100700 4.25060900 0.49844400 C 1.18573100 -0.38594500 -0.11130100 C 0.22153200 3.36130500 0.36706900 C 0.47468500 0.80919200 0.20417200 C 0.83331600 -0.87909200 0.10469600 C -0.96159100 0.82212700 0.31102700 C -0.53983400 -0.27012600 -0.09750400 C 0.49908200 3.20409300 0.79623700 C -0.71962300 1.07122700 -0.01092700 C -0.87079900 3.17503400 0.98272200 Sn -2.10759400 -1.71952800 -0.14724300 C -1.60167800 1.98577700 0.71930600 C -2.10130400 1.64385000 -0.09293300 C 0.42756700 -1.69797700 -0.02254100 C -3.00045700 1.47482800 0.97514200 C -1.04501400 -1.55238900 -0.28012000 C -4.31813200 1.95081700 0.87949000 C -1.71094500 -0.39680400 -0.06679100 C -4.74619700 2.60484000 -0.28577400 C -3.19044700 -0.34629800 -0.25487100 C -3.84803100 2.79018500 -1.35050200 C -4.01306000 -1.30111000 0.37057200 C -2.53228100 2.31689700 -1.25114200 C -5.40046300 -1.29586000 0.16189000 C -1.13325300 -3.52610200 -0.73413500 C -5.98312700 -0.33391700 -0.67655400 H -0.66103800 -3.42640700 -1.71875600 C -5.16933500 0.62221700 -1.30600900 H -0.36111600 -3.77959000 0.00305400 C -3.78456500 0.61717800 -1.09443100 C -2.95576500 -1.98860500 1.78826500 H 0.84785800 -2.44743800 -0.70547400 H -3.81461900 -1.32497600 1.93813800 H -3.55973300 -2.03366700 1.03228500 H -2.19239100 -1.76472600 2.54144200 H -5.61144700 1.36420300 -1.96326900 C -3.61540800 -1.18868000 -1.55405100 H -3.15564300 1.34929000 -1.59323600 H -4.15569600 -0.29817400 -1.20955700 H -6.02301100 -2.03496600 0.65585900 H -3.17389600 -0.96159100 -2.53098500 H -7.05622100 -0.32819200 -0.83799900 H 0.96465500 -1.72958400 -0.58053600 H -2.68068600 1.99278800 0.83111700 H -2.66077700 0.97437600 1.87829900 C 2.59980700 2.03738700 0.16817400 H -4.17442000 3.29456400 -2.25433800 C 2.57025100 -0.34088300 -0.38940100 H -1.83700200 2.44928100 -2.07539300 C 4.77268200 1.01597200 -0.52108200 H -5.00440500 1.81135900 1.70871500 C 5.42686000 -0.26903200 -0.94324200 H -5.76569400 2.96836200 -0.36406400 C 3.31902400 -1.50132900 -0.80971100 H -0.78879100 3.75561000 0.40495200 C 4.71034900 -1.43588500 -1.07667800 C 4.17827600 1.87573000 0.05564200 H 6.49255400 -0.25007900 -1.15238600 C 3.31578800 -0.38695100 -0.26647200 H 2.81407000 -2.44846500 -0.95215700 C 5.85986200 0.08415900 -0.39115300 C 3.27957300 0.91468400 -0.24550600 C 6.01525200 -1.36609700 -0.75129200 H -1.40016000 4.06479000 1.30639100 C 3.60657200 -1.76044200 -0.60170400 C 1.19270500 2.02724000 0.39429700 C 4.93047300 -2.20637700 -0.84715700 H 1.06251600 4.11938000 0.95460300 H 7.01883100 -1.73782500 -0.93713300 H 3.13932700 2.97227700 0.31159600 H 2.79870800 -2.47308500 -0.71019000 H 5.21957800 -2.34006300 -1.39664400 C 4.42233100 0.54606300 -0.20100800 H 4.94274100 1.77786400 -1.29750500 H 1.13617700 5.30825100 0.65310400 H 5.27901500 1.40603400 0.37547400 C 2.85571500 2.38365700 0.20561500 O 0.48835900 -2.24819800 1.34623000 H 3.46346300 4.44920700 0.46887500 C 1.78261700 -2.73071100 1.77835500 H 5.01137800 2.57363800 0.12340400 H 2.15490700 -3.51967400 1.10911000 H -3.28917200 -3.02370900 1.92516900 H 2.52302400 -1.92342000 1.82770100 H -1.84538800 -4.35783200 -0.78140900 H 1.62728100 -3.14520700 2.77547200 H -4.33522100 -2.00599500 -1.67982300 H -1.58230300 -2.44642800 -0.58185700 H 5.08445700 -3.24636600 -1.11895800 H 6.33851500 0.70403900 -1.16409400 rad_OMe_10CH2_Sn: H 6.42710800 0.29087500 0.53054100 E = -1123.081272 O 0.70401800 -1.43541800 1.47214800 C 1.75072300 -2.32648800 1.92630000

137 H 1.45987200 -2.64722100 2.92612000

rad_OMe_10CH2_H: E = -1000.638719

0 2

C 1.99806900 0.10022400 -0.01936600 0 2 C 1.74640600 1.49332900 0.13810700 C -1.18185500 -0.37443600 0.09857700 C 0.40284400 2.00526600 0.17847600 C -0.46757100 0.82023200 -0.20633900 C 2.58398900 3.79834700 0.41116800 C 0.96834600 0.82418200 -0.31121700 C 1.28158300 4.26670500 0.50248500 C -0.47471700 3.21826300 -0.78350100 C 0.19357800 3.36960400 0.36746100 C 0.89891700 3.18074300 -0.97077700 C 0.84064800 -0.86738000 0.11029200 C 1.61866000 1.98725200 -0.71455800 C -0.53654200 -0.27010900 -0.09585500 C -0.43520800 -1.68908200 0.00080200 C -0.72572900 1.07076200 -0.01329600 C 1.03706100 -1.55488000 0.26370000 Sn -2.09408700 -1.72994500 -0.14212700 C 1.70944000 -0.40056700 0.06048400 C -2.11125800 1.63335700 -0.10069500 C 3.18833600 -0.35910000 0.25584800 C -3.01160600 1.46321600 0.96617100 C 4.00892800 -1.31718500 -0.36731300 C -4.33180200 1.93123900 0.86603400 C 5.39519200 -1.32033800 -0.15129800 C -4.76129200 2.57824500 -0.30262200 C 5.97897700 -0.36353200 0.69228800 C -3.86207700 2.76455600 -1.36629500 C 5.16726900 0.59581600 1.31951500 C -2.54380900 2.29932300 -1.26237600 C 3.78360700 0.59898400 1.10077200 C -1.10901300 -3.53298700 -0.72233400 H -0.86442100 -2.44008500 0.67744100 H -0.63827400 -3.43442000 -1.70778100 H 3.55511400 -2.04562200 -1.03325400 H -0.33485300 -3.77754300 0.01574400 H 5.60999800 1.33403700 1.98060100 C -2.94246700 -1.99696600 1.79364400 H 3.15631900 1.33377100 1.59774600 H -3.80684900 -1.33948700 1.93899300 H 6.01605400 -2.06194500 -0.64366700 H -2.18180700 -1.76289900 2.54647800 H 7.05124000 -0.36410900 0.85923100 C -3.60474300 -1.21341400 -1.55140300 H 2.69755900 1.98488400 -0.82756600 H -4.15007200 -0.32477100 -1.21000000 C -2.58862700 2.07155500 -0.16737500 H -3.16443800 -0.98705200 -2.52906100 C -2.58017000 -0.32577400 0.38527300 H 0.98262100 -1.71807100 -0.57393600 C -4.71657500 1.01258300 0.50282800 H -2.67079000 0.96852300 1.87208200 C -5.42836600 -0.05873000 0.90422700 H -4.18948400 3.26364900 -2.27269800 C -3.32526300 -1.44746200 0.80342700 H -1.84739300 2.43297100 -2.08545600 C -4.79540000 -1.40989900 1.11416800 H -5.01888000 1.79130900 1.69451200 H -6.49496400 0.02809000 1.09293800 H -5.78262200 2.93584400 -0.38422700 C -3.27498100 0.95178200 0.23662100 H -0.82093800 3.75309700 0.40390700 H -5.20386100 1.97469200 0.36433600 C 4.17142800 1.92255900 0.06733900 H 1.43367900 4.06879600 -1.29001500 C 3.32804000 -0.36390500 -0.27025300 C -1.17615500 2.04922300 -0.39068500 C 5.80076800 0.12802300 -0.39869400 H -1.02999300 4.13933900 -0.93688500 C 6.09476000 -1.15121700 -0.70193600 H -3.12205500 3.00989400 -0.30540500 C 3.63454900 -1.69884100 -0.60259700 H -5.32312000 -2.16280800 0.50497800 C 5.02712100 -2.20219800 -0.86231400 H -4.96068000 -1.73485900 2.15528700 H 7.12637800 -1.46027000 -0.84686300 H -2.83410700 -2.40439700 0.94399300 C 4.42594200 0.59836800 -0.19529200 O -0.49570900 -2.23582300 -1.37140400 H 6.59406900 0.86486100 -0.29805900 C -1.79831400 -2.67679600 -1.82143000 H 1.08855300 5.32272200 0.65768600 H -2.20942500 -3.44641200 -1.15177600 C 2.83778000 2.41669400 0.21336600 H -2.50825100 -1.84415700 -1.89025600 H 3.42485900 4.48283600 0.48030000 H -1.64132300 -3.10595500 -2.81217400 H 4.99840800 2.62622700 0.13913200 H 1.56871900 -2.45357600 0.56145900 H -3.26762200 -3.03402200 1.93557400 H -1.81589900 -4.36940700 -0.76529300 rad_OMe_11aCHR_Sn: H -4.31993300 -2.03520400 -1.67440100 E = -1123.093975 H 5.24419500 -3.05341100 -0.19521700 H 5.08229300 -2.62905600 -1.87790700 H 2.83868000 -2.42757500 -0.71207000 O 0.71019500 -1.43052900 1.47713000 C 1.76932600 -2.30262300 1.93797700 H 1.88907700 -3.16912200 1.27141000 H 2.72466500 -1.77208800 2.01720400 138 O 0.56789300 -1.82707400 1.29717500 C 1.56389400 -2.83543500 1.58727200 H 1.65903100 -3.55011700 0.75829600 H 2.54562700 -2.39091800 1.79297700 H 1.20918000 -3.35877300 2.47621500 H 2.17577500 -0.08454300 1.58130100

rad_OMe_11aCHR_H: E = -1000.648763

0 2 C 2.04155300 0.00524200 0.48474300 C 1.78932800 1.49746900 0.27583300 C 0.49374600 2.02500600 0.13920900 C 2.69229500 3.77734100 0.39681800 C 1.40250700 4.29320300 0.29847900 C 0.30863900 3.42404300 0.15505600 0 2 C 0.83524600 -0.91150000 0.17497200 C 1.24539600 -0.38864500 0.42330000 C -0.51403000 -0.24213800 -0.00113200 C 0.46938800 0.91473000 0.22337500 C -0.66613100 1.10194000 0.01275500 C -0.92600300 0.94397100 0.04453000 Sn -2.09385400 -1.68238600 -0.13259200 C 0.49047700 3.36982800 0.31578700 C -2.03953500 1.69206400 -0.08336800 C -0.88881500 3.39057300 0.12816800 C -2.46670800 2.35048500 -1.25117000 C -1.59209100 2.18519300 -0.02722400 C -3.77317300 2.84882400 -1.34957800 C 0.47018600 -1.68282800 0.07176500 C -4.66621800 2.70376100 -0.27451300 C -1.01177400 -1.50772400 -0.11708800 C -4.24355900 2.06001200 0.89839600 C -1.67095800 -0.33359300 -0.09788200 C -2.93582400 1.55769700 0.99241000 C -3.16061900 -0.33152300 -0.20636500 C -1.21436200 -3.44522100 -0.95638800 C -3.79602200 -0.95837400 -1.29339300 H -0.66086200 -3.21987300 -1.87627900 C -5.19625400 -1.01040000 -1.37120000 H -0.52726200 -3.90018900 -0.23421800 C -5.97908200 -0.43639100 -0.35937600 C -2.92287800 -2.08086100 1.78590500 C -5.35289600 0.18958100 0.73151400 H -3.74343100 -1.39001200 2.00957600 C -3.95515500 0.24356000 0.80530700 H -2.13700700 -1.96232000 2.53900100 H 0.88731600 -2.15458800 -0.83126900 C -3.61325700 -1.03265600 -1.48039300 H -3.18776100 -1.39472100 -2.08055300 H -4.18875600 -0.20089800 -1.05696500 H -5.95148600 0.62791900 1.52363900 H -3.17283700 -0.69220000 -2.42488100 H -3.47303300 0.71444200 1.65754800 H 1.03872500 -1.51902100 -0.72086300 H -5.67211700 -1.49424400 -2.21811300 H -1.77724300 2.45227800 -2.08490900 H -7.06201500 -0.47615300 -0.41750100 H -4.92659900 1.94872900 1.73445400 H -2.66069600 2.20806900 -0.20814000 H -2.60110100 1.06314900 1.90092000 C 2.62348500 2.11654200 0.38104600 H -4.09632300 3.34166000 -2.26087600 C 2.66492600 -0.29880900 -0.14782700 H -5.67797900 3.08841500 -0.35169200 C 4.72866500 1.03045900 -0.33922500 H -0.69331800 3.83080300 0.07259900 C 5.40782000 -0.07159200 -0.85708000 C 4.23337500 1.83548200 0.36140000 C 3.36015200 -1.38194000 -0.69648100 C 3.37721400 -0.43564300 -0.12303000 C 4.71511500 -1.27757300 -1.05848700 C 5.77256400 0.05548400 -0.40934800 H 6.45819500 0.00500600 -1.11750900 C 5.98878700 -1.22456900 -0.91875100 C 3.35228300 0.94617300 -0.00516500 C 3.61419400 -1.70501000 -0.66202100 H 5.24102600 1.97991600 -0.20945800 C 4.90143300 -2.10242000 -1.06590900 H -1.42114600 4.33481100 0.08699300 H 6.98557200 -1.53525600 -1.21325700 C 1.19027800 2.13563600 0.33737000 C 4.47262200 0.47828600 -0.03021100 H 1.05051600 4.29566700 0.41266400 H 6.59766300 0.75690300 -0.31901300 H 3.15919600 3.05176700 0.52358600 H 1.23989300 5.36544000 0.32295500 H 5.22544300 -2.13538400 -1.48374000 C 2.90492900 2.37432400 0.37220100 H 2.86512300 -2.33268100 -0.85228800 H 3.54954700 4.43997800 0.47712200 O 0.53720900 -2.64428100 1.17549000 H 5.07793100 2.51057300 0.47609700 C 1.81630700 -3.26502400 1.43661900 H -3.30918800 -3.10507000 1.83904100 H 2.14234000 -3.87871500 0.58558400 H -1.99048200 -4.17930400 -1.20354100 H 2.59453400 -2.52545900 1.66553500 H -4.30278500 -1.85736000 -1.69906300 H 1.66141500 -3.90785200 2.30393700 H 5.05205000 -3.09285200 -1.48256600 H 1.37819500 -0.45286300 1.52161900 H 2.80384100 -2.41460900 -0.77804100 H -1.56156100 -2.44166700 -0.19837600

139 Additional Information

Table 14. Optimization of the Sn‐promoted radical cyclization of alkyne 6a.a Entry Reagent Initiator Ratio by NMR spectroscopyb

(equiv) (equiv) 1 3 4

1 HSnBu3 (2) AIBN (0.1) 71 20 9

2 HSnBu3 (2) AIBN (0.2) 65 22 12

3 HSnBu3 (2) AIBN (0.3) 38 35 27

4 HSnBu3 (2) AIBN (0.5) 23 45 32

5 HSnBu3 (2) AIBN (1) 0 66 34

6 HSnBu3 (1) AIBN (1) 90 10 <1 aSee the Supporting Information for the reaction scale and reagent concentrations. bCompound 5 appeared after exposure of the mixtures to silica gel.

140 APPENDIX D

CHAPTER FOUR SUPPORTING INFORMATION

Computational Details

All computations were performed in Gaussian 09 with unrestricted M06-2X functional[105,174] due to its relatively accurate description of reaction and activation energies for a variety of chemical processes including radical reactions.[175] The LanL2DZ basis set was used for all atoms. Chemcraft 1.7 and CYLView were used to render the orbitals and molecules. Frequency calculations were performed to confirm each stationary point as either a minimum or a first-order saddle point. Intrinsic Reaction Coordinates (IRC)[176] were determined for the TS of interest. We performed Natural Bond Orbital [177–187] (NBO) analysis on key intermediates and transition states.

(1a) nap_SM_HH E = -501.6333827 No. of Negative Frequencies = 0

C -0.2261870000 2.7801440000 0.1645780000 C -1.3527190000 1.9670580000 -0.1390780000 C 1.0300610000 2.2125460000 0.2863360000 C 2.2466930000 -0.3625410000 -0.6634940000 C -1.2053460000 0.6060540000 -0.3666430000 H 2.2525630000 0.3392580000 -1.5042610000 C 0.0954280000 0.0217690000 -0.3180180000 H 2.8520270000 -1.2267280000 -0.9617020000 C 1.2156720000 0.8157690000 0.0660340000 C 2.9071360000 0.2941270000 0.5423320000 C 2.4917660000 0.1901110000 0.2399120000 C 3.4466940000 1.5072700000 0.5388160000 H 3.3381520000 0.8016430000 0.5404170000 C 0.8390900000 -0.8408610000 -0.3500020000 C 2.6457820000 -1.1715230000 0.0273620000 C 0.5909150000 -2.1921390000 -0.1777650000 C 1.5536400000 -1.9598990000 -0.4144690000 C -0.2424960000 0.0966800000 -0.2066470000 C 0.2793610000 -1.3907650000 -0.5690890000 C -0.7105220000 -2.6753570000 0.1443740000 H 1.8872580000 2.8197870000 0.5639420000 H 1.4055190000 -2.9022670000 -0.2928400000 H 3.6183390000 -1.6346570000 0.1613500000 C -1.5504650000 -0.3889800000 0.1131820000 H 1.7082040000 -3.0065040000 -0.6553970000 C -1.7595340000 -1.7912140000 0.2874490000 H -0.4542620000 -1.9189410000 -1.1717980000 H -0.8680900000 -3.7411910000 0.2727250000 C -2.3973170000 -0.3144110000 -0.5146960000 H -2.7568750000 -2.1467580000 0.5312890000 H -3.3243650000 0.2613250000 -0.4482950000 C -2.4250230000 1.8917050000 0.0749180000 C -2.3882410000 -1.4054130000 0.5691230000 C -1.1246430000 2.3788880000 -0.2440180000 C -1.2880220000 -2.0713590000 0.9119350000 C -0.0619890000 1.5047550000 -0.3793860000 H -2.3431910000 2.4126560000 -0.1654530000 C -2.6288480000 0.5366610000 0.2489630000 H -0.3651700000 3.8431370000 0.3328040000 H -3.2493560000 2.5894950000 0.1791750000 H -2.3950890000 -0.7996730000 -1.5016980000 H -0.9711750000 3.4446260000 -0.3789650000 H -3.3434560000 -1.6052150000 1.0597200000 H 0.9249980000 1.8923640000 -0.6101430000 H -1.0496900000 -2.8540390000 1.6246840000 H -3.6164350000 0.1530660000 0.4909030000 H 2.9131580000 -0.3103690000 1.4556530000 H 3.9516280000 2.1545500000 1.2458250000 (1c) nap_P_HH E = -501.6796873 No. of Negative Frequencies = 0 (1b) nap_TS_HH E = -501.6174492 No. of Negative Frequencies = 1 freq = -575.0499

141 C 4.2369900000 0.0071250000 -0.4125700000 H 5.0763990000 -1.9577770000 -0.5915330000 H 5.1468480000 0.5242590000 -0.7046510000 C 1.9859110000 2.9495850000 0.1637740000 C 0.7835700000 2.2918520000 0.5532630000 C 0.7288610000 0.9115740000 0.6160650000 C 3.1068960000 2.2049610000 -0.1483290000 H 2.0158120000 4.0332500000 0.1180980000 H -0.0936180000 2.8796370000 0.8057770000 H -0.1965190000 0.4312740000 0.9181680000 H 4.0310740000 2.6953950000 -0.4421950000 H -0.0649630000 -2.6208670000 -1.3573070000 C 2.3371440000 0.8774950000 0.2290240000 H 3.2807790000 0.6286860000 -0.2671370000 H 2.5826560000 1.0631140000 1.2865620000 (2b) nap_TS_HPh C 1.7352770000 2.1372400000 -0.3654420000 E = -732.5643667 C 0.4138300000 2.3617990000 -0.2969850000 No. of Negative Frequencies = 1 C 1.3778500000 -0.2978410000 0.1326870000 freq = -485.2804 C 1.8546400000 -1.6107640000 -0.0176360000 C -0.0040870000 -0.0607480000 0.1747670000 C 0.9558830000 -2.6870740000 -0.1222220000 H 2.9253780000 -1.7913650000 -0.0559780000 C -0.9220750000 -1.1342800000 0.0258560000 C -0.4198500000 -2.4516790000 -0.1087500000 H 1.3343750000 -3.6982550000 -0.2302830000 H -1.1201240000 -3.2753350000 -0.2170970000 C -2.8145270000 0.4703190000 -0.0817850000 C -1.9610000000 1.5445390000 0.0672540000 C -0.5013880000 1.3618100000 0.3981840000 C -2.3397610000 -0.8623350000 -0.0443710000 C 4.0096440000 -0.2303290000 -1.1018140000 H -3.8728260000 0.6489490000 -0.2471260000 C 3.3404500000 -1.3858350000 -0.6125290000 H -2.3383680000 2.5629610000 0.0146300000 C 3.4943690000 1.0305870000 -0.8554000000 H -0.3983430000 1.5607110000 1.4856260000 C 2.1971790000 -1.2655900000 0.1645840000 H -3.0295440000 -1.6948510000 -0.1460560000 C 1.7044640000 0.0301000000 0.4967940000 H 2.4010860000 2.8490600000 -0.8450250000 C 2.3157250000 1.1875880000 -0.0675640000 H -0.0366960000 3.2554340000 -0.7215950000 C 1.7186650000 2.4704830000 0.1519540000 H 2.1859250000 3.3480010000 -0.2864490000 C 0.5627730000 2.5911390000 0.9113260000 (2a) nap_SM_HPh C -0.0177510000 1.4558630000 1.5282320000 E = -732.5812074 C 0.5231560000 0.1757310000 1.3180950000 No. of Negative Frequencies = 0 H 3.9716300000 1.9141900000 -1.2700640000 H 0.1166310000 3.5681570000 1.0684400000 H -0.8807650000 1.5749040000 2.1750400000 H 0.2617340000 -0.6182570000 2.0131500000 C 1.3444720000 -2.4584240000 0.5408570000 H 1.7904840000 -3.3770530000 0.1511670000 C -0.0749020000 -2.2949580000 -0.0286120000 C -0.7901680000 -1.1836730000 0.1049640000 C -2.0773430000 -0.6080160000 -0.1801280000 C -3.2626360000 -1.1562240000 0.3690440000 C 0.5692060000 -2.0625280000 0.7023720000 C -2.1660180000 0.5736610000 -0.9557370000 H 0.0807570000 -1.6223750000 1.5770990000 C -4.5022250000 -0.5546270000 0.1204200000 H 0.8109200000 -3.1018200000 0.9508750000 H -3.1968500000 -2.0508660000 0.9810520000 C -0.4068220000 -2.0618700000 -0.4823270000 C -3.4083540000 1.1668220000 -1.2027550000 C -1.5566240000 -1.4250280000 -0.5086200000 H -1.2535620000 1.0082610000 -1.3543210000 C -2.6931050000 -0.6441720000 -0.3164970000 C -4.5814990000 0.6060360000 -0.6674110000 C -2.6933470000 0.7443290000 -0.6783690000 H -5.4054760000 -0.9878240000 0.5381660000 C -3.8997500000 -1.2027260000 0.2175210000 H -3.4640030000 2.0666460000 -1.8069330000 C -3.8384010000 1.5186690000 -0.5048390000 H -5.5438110000 1.0705200000 -0.8566610000 H -1.7870260000 1.1741050000 -1.0946890000 H 3.7112000000 -2.3719730000 -0.8773300000 C -5.0328660000 -0.4095030000 0.3841580000 H 4.9070780000 -0.3459880000 -1.7008620000 H -3.9135000000 -2.2535490000 0.4884820000 H 1.2852120000 -2.5697010000 1.6326240000 C -5.0154750000 0.9541390000 0.0270790000 H -0.4654280000 -3.1310330000 -0.6129450000 H -3.8226470000 2.5671220000 -0.7857510000

H -5.9384170000 -0.8473980000 0.7918080000

H -5.9032590000 1.5635870000 0.1574260000 (2c) nap_P_HPh C 1.8474730000 -1.3238620000 0.3487110000 E = -732.6144191 C 2.9944150000 -2.0324430000 0.0332470000 No. of Negative Frequencies = 0 C 1.8711950000 0.1138430000 0.2950020000 C 4.1967300000 -1.3702770000 -0.3500490000 H 2.9787840000 -3.1182150000 0.0780810000 C 3.0783670000 0.7785630000 -0.0912050000 142 H -6.2634260000 0.2274810000 1.1455550000 H -6.4345150000 2.0473050000 -0.5512580000 C 1.9726610000 0.0756700000 1.4193310000 C 2.9059590000 -0.9441870000 1.5075310000 C 2.2672830000 1.2301210000 0.6134830000 C 4.1487290000 -0.8784970000 0.8115880000 H 2.6847470000 -1.8154360000 2.1191560000 C 3.5087850000 1.2911940000 -0.0946870000 C 4.4413520000 0.2153290000 0.0228470000 H 4.8573610000 -1.6946490000 0.9057780000 C -1.1348290000 -2.4576760000 0.3862250000 H 5.3814760000 0.2743620000 -0.5186710000 H -1.3965100000 -3.3703300000 -0.1565650000 C 2.8878840000 3.4609600000 -1.0288090000 H -1.2301450000 -2.6898780000 1.4599730000 C 1.6554730000 3.4089240000 -0.3155430000 C 0.2934900000 -2.0430210000 0.0893730000 C 1.3531960000 2.3219280000 0.4844100000 C 0.7050110000 -0.7799590000 0.3172980000 C 3.7940470000 2.4241740000 -0.9146060000 C 2.0961250000 -0.3484560000 0.0086610000 H 3.1110310000 4.3182450000 -1.6554590000 C 2.3490440000 0.7805770000 -0.7973350000 H 0.9530250000 4.2317770000 -0.4010920000 C 3.1902270000 -1.1005820000 0.4796280000 Sn -0.2003960000 -1.6461600000 -0.5323180000 C 3.6620340000 1.1458070000 -1.1221230000 C -2.1217150000 -1.9155490000 -1.4027330000 H 1.5136720000 1.3580410000 -1.1823680000 H -2.8228480000 -2.3331650000 -0.6711900000 C 4.5054550000 -0.7362450000 0.1547210000 H -2.5272520000 -0.9546860000 -1.7407030000 H 3.0026100000 -1.9638020000 1.1120290000 H -2.0739350000 -2.5927710000 -2.2632970000 C 4.7458580000 0.3894780000 -0.6464670000 C 1.1727930000 -0.8130830000 -1.9297720000 H 3.8398220000 2.0125480000 -1.7507490000 H 0.9946970000 0.2621790000 -2.0476900000 H 5.3371020000 -1.3250460000 0.5285530000 H 2.2014080000 -0.9494460000 -1.5741690000 H 5.7625340000 0.6740370000 -0.8979370000 H 1.0735290000 -1.2937550000 -2.9101970000 C -2.0976270000 -1.3366400000 0.0350040000 C 0.5642080000 -3.4793300000 0.2529900000 C -3.3512610000 -1.5802690000 -0.5450620000 H 0.2022770000 -3.6504410000 1.2731260000 C -1.6869230000 -0.0208800000 0.2906590000 H 0.2490100000 -4.3256810000 -0.3680260000 C -4.1996590000 -0.5048200000 -0.8694110000 H 1.6593000000 -3.4523630000 0.2707360000 H -3.6626570000 -2.6010490000 -0.7481350000 H 0.4100080000 2.2943670000 1.0198470000 C -2.5253790000 1.0723870000 -0.0458200000 H 4.7390350000 2.4555990000 -1.4500850000 C -3.7905690000 0.8070970000 -0.6268860000

H -5.1691120000 -0.6971630000 -1.3175700000

H -4.4365070000 1.6410500000 -0.8873570000 (3b) nap_TS_SnPh C -0.7779370000 2.6621560000 0.7103720000 E = -855.0104733 C 0.0807240000 1.6318180000 1.0421720000 No. of Negative Frequencies = 1 C -0.3262340000 0.1843080000 0.9449870000 freq = -426.1873 C -2.0702860000 2.4226090000 0.1888960000 H -0.4485670000 3.6875060000 0.8503240000 H 1.0656610000 1.8471890000 1.4460280000 H -0.4249510000 -0.1789400000 1.9895880000 H -2.7250040000 3.2512730000 -0.0635310000 H 0.9684800000 -2.7715700000 -0.3516370000

(3a) nap_SM_SnPh E = -855.0310398 No. of Negative Frequencies = 0

C -3.3557650000 -2.9479680000 0.9179780000 C -2.1841620000 -2.9657880000 0.1132650000 C -4.1122550000 -1.7926560000 1.0218190000 C -1.8153640000 -1.8479340000 -0.6243830000 C -2.6288630000 -0.6780880000 -0.5882050000

C 0.6291140000 -0.0570320000 2.1128360000 C -3.7520790000 -0.6232440000 0.2883030000 H 0.4127040000 0.8170140000 2.7392120000 C -4.4716670000 0.6069960000 0.4272900000 H 0.6592750000 -0.9313840000 2.7745630000 H -5.3259210000 0.6416790000 1.0977940000 C -0.5101390000 -0.2557230000 1.0995510000 C -4.0837780000 1.7359260000 -0.2830510000 C -1.6500340000 0.3934830000 1.1097060000 C -3.0049050000 1.6786690000 -1.1979860000 C -2.9152910000 0.8186750000 0.6725390000 C -2.2579570000 0.4958100000 -1.3480400000 C -3.0325720000 1.8654090000 -0.2947740000 H -4.9807770000 -1.7579950000 1.6738640000 C -4.1147290000 0.2408090000 1.1901890000 H -4.6342510000 2.6643990000 -0.1681480000 C -4.2879300000 2.2937930000 -0.7266170000 H -2.7563770000 2.5497720000 -1.7953060000 H -2.1258150000 2.3129280000 -0.6922440000 H -1.6545890000 0.3767920000 -2.2445950000 C -5.3616710000 0.6817250000 0.7472810000 C -0.4802150000 -1.7524240000 -1.3283150000 H -4.0372260000 -0.5492260000 1.9305320000 H 0.0552590000 -2.7032510000 -1.2401470000 C -5.4614680000 1.7088490000 -0.2119020000 C 0.3486800000 -0.5972460000 -0.7162930000 H -4.3596770000 3.0839010000 -1.4675700000 C -0.1600560000 0.6200360000 -0.5798760000 C 0.2087340000 1.9513040000 -0.1712020000 143 C 1.2440310000 2.6489750000 -0.8427930000 C 3.5966050000 2.4576090000 -0.2879370000 C -0.4832390000 2.5997280000 0.8798510000 C 2.3656470000 2.2079380000 -0.8646110000 C 1.6016180000 3.9424810000 -0.4444790000 C 1.8346340000 0.8107450000 -1.0511100000 H 1.7533580000 2.1656290000 -1.6725470000 C 4.4108590000 1.4198850000 0.2223690000 C -0.1171320000 3.8909320000 1.2748630000 H 3.9478540000 3.4830700000 -0.2200440000 H -1.2940290000 2.0747510000 1.3773210000 H 1.7636190000 3.0276230000 -1.2461130000 C 0.9278010000 4.5668740000 0.6190400000 Sn -2.0610600000 -1.1902600000 0.1140910000 H 2.4023430000 4.4635540000 -0.9598470000 C -2.4904790000 -0.0560560000 1.8615160000 H -0.6449010000 4.3737480000 2.0911390000 H -1.6167480000 -0.0368990000 2.5224310000 H 1.2069970000 5.5689220000 0.9276360000 H -2.7364860000 0.9789950000 1.5953060000 Sn 2.2866050000 -0.9897760000 0.1266540000 H -3.3347710000 -0.4884450000 2.4108740000 C 2.3167620000 -3.0752270000 0.5751740000 C -3.5876110000 -0.9054210000 -1.3526870000 H 3.1808330000 -3.3252780000 1.2012250000 H -4.0058970000 0.1044710000 -1.2729420000 H 1.4077360000 -3.3635140000 1.1159370000 H -3.1871760000 -1.0373630000 -2.3642440000 H 2.3781530000 -3.6723130000 -0.3420400000 H -4.3990700000 -1.6278760000 -1.2078700000 C 3.8211380000 -0.5340630000 -1.2825710000 C -1.9544190000 -3.2703320000 0.5826140000 H 4.7875330000 -0.9188660000 -0.9369370000 H -1.0992740000 -3.4830550000 1.2350910000 H 3.6029030000 -0.9791650000 -2.2594020000 H -2.8648390000 -3.5901880000 1.1028690000 H 3.9107980000 0.5507910000 -1.4088050000 H -1.8545160000 -3.8761770000 -0.3258820000 C 2.5112780000 0.2031740000 1.8704890000 H 1.8365900000 0.6077150000 -2.1428790000 H 3.4237390000 -0.0633790000 2.4156920000 H 5.3747590000 1.6439210000 0.6695860000 H 2.5637740000 1.2637020000 1.5987510000 H 1.6534250000 0.0674250000 2.5380620000 H -1.5572720000 -3.8534260000 0.0959950000 (4a) biph_SM_HH H -3.6334240000 -3.8348640000 1.4783780000 E = -539.7191066 H -0.6111840000 -1.5578870000 -2.4019700000 No. of Negative Frequencies = 0

(3c) nap_P_SnPh E = -855.0543927 No. of Negative Frequencies = 0

C 1.0404400000 -1.7775340000 0.2367000000 C 0.5405560000 -0.4750610000 0.0340030000 C 1.4553860000 0.5947290000 -0.1260270000 C 2.8395370000 0.3313100000 -0.0504180000 C 3.3208130000 -0.9616040000 0.1674100000 C 2.4149280000 -2.0272230000 0.3031100000 H 0.3344890000 -2.5918350000 0.3722460000 C 0.8527150000 -1.7973520000 -1.0341660000 H 3.5318580000 1.1575690000 -0.1866490000 H 0.4737000000 -2.7881330000 -0.7624100000 H 4.3893010000 -1.1426020000 0.2206800000 H 0.9519180000 -1.7889960000 -2.1332150000 H 2.7772480000 -3.0366300000 0.4672620000 C -0.1204250000 -0.6842150000 -0.6305630000 C -2.9389450000 0.8495010000 0.8592770000 C 0.3593120000 0.5837720000 -0.6344160000 C -3.7480690000 0.0278750000 0.0579380000 C -0.4845670000 1.7514140000 -0.2506380000 C -3.1531970000 -0.9494310000 -0.7544330000 C -1.6458150000 2.0656030000 -0.9818880000 C -1.7594360000 -1.1015940000 -0.7670800000 C -0.1620440000 2.5285670000 0.8805040000 C -0.9381210000 -0.2766280000 0.0259630000 C -2.4822460000 3.1199140000 -0.5805910000 C -1.5458620000 0.6972540000 0.8434070000 H -1.8844790000 1.4865450000 -1.8705630000 H -3.3913370000 1.5996490000 1.4998940000 C -0.9967540000 3.5779290000 1.2846040000 H -4.8266320000 0.1463780000 0.0691890000 H 0.7324390000 2.2906820000 1.4495640000 H -3.7713240000 -1.5867790000 -1.3786300000 C -2.1627770000 3.8751270000 0.5574020000 H -1.2998050000 -1.8485850000 -1.4084920000 H -3.3745950000 3.3502110000 -1.1541830000 H -0.9232010000 1.3196550000 1.4802800000 H -0.7453890000 4.1578490000 2.1668070000 C 0.9898290000 1.9706820000 -0.4336520000 H -2.8093230000 4.6876970000 0.8724310000 C 1.7498530000 3.0634230000 -0.3649420000 C 2.2202740000 -1.5708010000 -0.4157490000 H -0.0479370000 2.0682360000 -0.7637680000 C 2.9785340000 -2.6012760000 0.1587910000 H 1.6210670000 4.1207500000 -0.5595420000 C 2.7057120000 -0.2563850000 -0.4079130000 C 4.2296550000 -2.3146190000 0.7381070000 H 2.5972300000 -3.6184870000 0.1583880000 (4b) biph_TS_HH C 3.9546330000 0.0500890000 0.1872090000 E = -539.7068721 C 4.7120500000 -1.0048320000 0.7555260000 No. of Negative Frequencies = 1 H 4.8152540000 -3.1141170000 1.1804280000 freq = -530.4411 H 5.6712630000 -0.7798670000 1.2137840000

144 C -1.4287760000 -1.5875720000 -0.1846290000 C -0.6955360000 -0.4392990000 0.1038460000 C -1.4195300000 0.8364700000 0.4985590000 H -3.4273670000 1.7657870000 0.2411850000 H -4.6197730000 -0.3213390000 -0.3246540000 H -3.3721460000 -2.4852840000 -0.5089360000 H -0.9043400000 -2.5096520000 -0.4191490000 H -1.3467310000 0.8958990000 1.6106350000 C 0.6097540000 2.0777200000 -0.2600150000 C -0.7137720000 2.0823580000 -0.0108260000 H 1.1184780000 2.9805470000 -0.5883110000 H -1.3087320000 2.9850550000 -0.1261080000

(5a) biph_SM_HPh E = -770.6660770 C -1.5053860000 -1.5540840000 0.3294850000 No. of Negative Frequencies = 0 C -0.7494690000 -0.3884880000 0.1167270000 C -1.4177920000 0.8349090000 -0.1539950000 C -2.8251000000 0.8500390000 -0.1898450000 C -3.5694320000 -0.3120490000 0.0459550000 C -2.9063790000 -1.5224120000 0.3021920000 H -0.9848300000 -2.4846900000 0.5377330000 H -3.3354590000 1.7839590000 -0.4110980000 H -4.6535960000 -0.2777240000 0.0224530000 H -3.4736520000 -2.4297800000 0.4811430000 C 2.8407630000 -1.3174690000 -0.7340670000 C 3.5559320000 -0.3604690000 0.0108140000 C 2.8727440000 0.5532460000 0.8181010000 C 3.3346330000 1.1125800000 0.0110980000 C 1.4529380000 0.5603820000 0.8487980000 C 2.1424470000 0.3706590000 0.0017330000 C 0.7332570000 -0.4305300000 0.1171660000 C 2.2058800000 -1.0447370000 -0.0070820000 C 1.4365410000 -1.3498130000 -0.6717660000 C 3.4675470000 -1.6715250000 -0.0062390000 H 3.3721580000 -2.0309910000 -1.3551090000 C 4.6503970000 -0.9228470000 0.0032230000 H 4.6406160000 -0.3460970000 -0.0266970000 C 4.5858290000 0.4780690000 0.0119030000 H 3.4227800000 1.2651210000 1.4252400000 H 3.2719230000 2.1967210000 0.0176900000 H 0.9451200000 1.0902080000 1.6509690000 H 3.5156130000 -2.7575640000 -0.0127640000 H 0.8813470000 -2.0760200000 -1.2592490000 H 5.6116040000 -1.4262760000 0.0038510000 C -0.6790920000 2.0758350000 -0.4933500000 H 5.4955810000 1.0692330000 0.0190450000 C 0.6239360000 2.2836940000 -0.2783890000 C -1.0422850000 2.0632370000 -1.2143360000 H -1.2807230000 2.8525310000 -0.9763440000 C -1.6771690000 2.3720150000 -0.0012470000 H 1.2854740000 3.1167450000 -0.4960020000 C -1.0492330000 2.0539120000 1.2129580000 C 0.1994260000 1.4160020000 1.2139550000 C 0.8295480000 1.0847900000 0.0009740000 (4c) biph_P_HH C 0.2061260000 1.4249990000 -1.2130600000 E = -539.7611965 H -1.5241810000 2.3077060000 -2.1556510000 No. of Negative Frequencies = 0 H -2.6508760000 2.8508610000 -0.0021640000 H -1.5367830000 2.2907320000 2.1533060000 H 0.6828150000 1.1547660000 2.1509760000 H 0.6949100000 1.1708880000 -2.1492420000 C -2.3531960000 -1.0804110000 -1.2312310000 C -3.7100350000 -0.7642420000 -1.2105220000 C -4.3938390000 -0.6088640000 0.0118970000 C -3.6973550000 -0.7835190000 1.2245560000 C -2.3404790000 -1.0998580000 1.2258280000 C -1.6281570000 -1.2547740000 -0.0077740000 H -1.8229670000 -1.1887990000 -2.1721030000 H -4.2426920000 -0.6349100000 -2.1474150000 H -5.4504610000 -0.3625080000 0.0192090000 H -4.2201630000 -0.6690260000 2.1689290000 C 1.5673530000 -1.5574680000 0.1875020000 H -1.8003650000 -1.2231290000 2.1591950000 C 0.7685980000 -0.3961560000 0.0764930000 C 0.9972300000 -1.9118740000 -0.0161050000 C 1.4172530000 0.8598550000 -0.0984010000 C -0.2678710000 -1.5325380000 -0.0153690000 C 2.8207920000 0.9189500000 -0.1657730000 H 1.2193770000 -2.9851390000 -0.0238270000 C 3.5958770000 -0.2394710000 -0.0506830000 C 2.9613050000 -1.4831040000 0.1287390000 H 1.0939400000 -2.5208950000 0.3489350000 (5b) biph_TS_HPh H 3.3007010000 1.8833290000 -0.3103910000 E = -770.6539426 H 4.6781670000 -0.1808050000 -0.0973120000 No. of Negative Frequencies = 1 H 3.5548850000 -2.3860120000 0.2284180000 freq = -449.8426 C -2.8931860000 0.8207930000 0.1720900000 C -3.5502050000 -0.3357530000 -0.1391010000 C -2.8344410000 -1.5750940000 -0.2668520000 145 C 0.0260540000 1.0152300000 0.3821690000 H 1.8898120000 2.0704180000 -0.2767130000 H 0.8158990000 4.2236330000 -0.7809060000 H -1.6727790000 4.4795330000 -0.5879100000 H -3.0824850000 2.4798030000 -0.3173360000 H 0.1014780000 1.0955070000 1.4948290000 C 2.7296810000 -1.3269410000 -0.9321770000 C 4.1168840000 -1.5262020000 -0.9121500000 C 4.9042420000 -0.9097680000 0.0721370000

C -3.6906720000 0.3587900000 -0.1787610000 C 4.2922090000 -0.0895830000 1.0335990000 C -2.3134240000 0.0893540000 -0.0925640000 C 2.9064420000 0.1121740000 1.0092910000 C -1.8761390000 -1.2412290000 0.1449500000 C 2.1035370000 -0.5110830000 0.0312570000 C -2.8388770000 -2.2613080000 0.2720540000 H 2.1262750000 -1.7847720000 -1.7107860000 C -4.2065390000 -1.9867370000 0.1592360000 H 4.5820670000 -2.1522750000 -1.6667650000 C -4.6363130000 -0.6680750000 -0.0608500000 H 5.9784210000 -1.0616390000 0.0875100000 H -4.0138870000 1.3795180000 -0.3634170000 H 4.8923660000 0.3898720000 1.8002490000 H -2.5049720000 -3.2769170000 0.4690160000 H 2.4439290000 0.7429350000 1.7641570000 H -4.9315800000 -2.7886180000 0.2514750000 C -0.1831360000 -1.4184090000 -0.1433280000 H -5.6948610000 -0.4449200000 -0.1429660000 C 0.6259700000 -0.3481910000 0.0384640000 C -0.4027810000 3.3279890000 0.4936580000 H 0.2565370000 -2.3986760000 -0.3168520000 C 0.7250290000 3.1274800000 -0.3276610000 C 0.8388320000 1.9652420000 -1.0929420000 C -0.1567260000 0.9524370000 -1.0093410000 (6a) biph_SM_SnPh C -1.3125030000 1.1742510000 -0.2011940000 E = -893.1091135 C -1.4147780000 2.3534640000 0.5487890000 No. of Negative Frequencies = 0 H -0.4912680000 4.2348470000 1.0829770000 H 1.4985530000 3.8873420000 -0.3792210000 H 1.6925870000 1.8195150000 -1.7469830000 H -0.2092830000 0.2029080000 -1.7962700000 H -2.2748950000 2.4963050000 1.1974210000 C -0.4504940000 -1.5715320000 0.3746950000 C 0.5964710000 -0.8004570000 0.0708750000 H -0.2703270000 -2.5219800000 0.8871870000 C 2.0347070000 -0.8390590000 0.1290980000 C 2.7391560000 0.1118200000 0.9073630000 C 2.7714470000 -1.7673420000 -0.6473280000 C 4.1375630000 0.1105780000 0.9314770000 H 2.1746550000 0.8379170000 1.4850710000 C 4.1713530000 -1.7589040000 -0.6219380000

H 2.2353460000 -2.4859010000 -1.2600560000 C -0.0088790000 -3.9887830000 -0.0100680000 C 4.8602760000 -0.8232500000 0.1678800000 C 0.2395790000 -2.6067470000 -0.0026660000 H 4.6658880000 0.8367710000 1.5408090000 C -0.8512040000 -1.6957330000 -0.0288190000 H 4.7253620000 -2.4792870000 -1.2152730000 C -2.1583400000 -2.2222530000 -0.0633390000 H 5.9451510000 -0.8185710000 0.1852540000 C -2.3968190000 -3.6022530000 -0.0696070000 C -1.3169780000 -4.4945330000 -0.0421450000 H 0.8386840000 -4.6675100000 0.0104480000 (5c) biph_P_HPh H -3.0103100000 -1.5464270000 -0.0947120000 E = -770.6973230 H -3.4153800000 -3.9751400000 -0.0974070000 No. of Negative Frequencies = 0 H -1.4881240000 -5.5658210000 -0.0466030000 C 3.6737030000 -1.4233670000 -1.1400920000 C 4.2916290000 -1.1334470000 0.0861570000 C 3.5981670000 -1.3617540000 1.2852100000 C 2.2876930000 -1.8581920000 1.2572100000 C 1.6539610000 -2.1243710000 0.0296720000 C 2.3630590000 -1.9207360000 -1.1679420000 H 4.2060760000 -1.2497240000 -2.0698610000 C -3.6900210000 -0.0588020000 0.2286780000 H 5.2987750000 -0.7303360000 0.1074290000 C -2.2798850000 -0.0871220000 0.1059430000 H 4.0734900000 -1.1427390000 2.2361520000 C -1.6392820000 -1.3503400000 -0.0285030000 H 1.7412280000 -2.0206500000 2.1818300000 C -2.4089230000 -2.5290390000 -0.0559930000 H 1.8741910000 -2.1291320000 -2.1153350000 C -3.8007280000 -2.4816120000 0.0594890000 C 2.1986760000 1.6927180000 -1.2770950000 C -4.4407240000 -1.2356210000 0.2079480000 C 3.3077220000 2.5359140000 -1.2718910000 H -4.2010090000 0.8884030000 0.3645660000 C 3.8661770000 2.9847150000 -0.0574340000 H -1.9034910000 -3.4848740000 -0.1659520000 C 3.2898300000 2.5770630000 1.1628300000 H -4.3836410000 -3.3962510000 0.0418260000 C 2.1808490000 1.7337850000 1.1799070000 H -5.5197540000 -1.1894960000 0.3133510000 C 1.6016120000 1.2678310000 -0.0455290000 C 0.8169920000 2.1879390000 -0.1658910000 H 1.7779310000 1.3341110000 -2.2117710000 C 0.2169300000 3.3804710000 -0.4505120000 H 3.7463730000 2.8482650000 -2.2146880000 C -1.2109310000 3.5205940000 -0.3793110000 H 4.7304110000 3.6404630000 -0.0621460000 C -2.0092960000 2.3823800000 -0.1838540000 H 3.7140060000 2.9214580000 2.1011190000 C -1.4632860000 1.1235720000 0.0755330000 H 1.7465460000 1.4059160000 2.1198130000 146 C -0.6487480000 -0.2131100000 -0.0271980000 H 1.9838110000 -0.5063900000 2.3257330000 C 0.5172180000 0.3979660000 -0.0386730000 H 2.9305370000 -2.0035610000 2.1581080000 C -3.6446050000 0.7846520000 -1.6051300000 C 1.7869080000 -2.9827280000 -1.3449150000 H -4.5020640000 0.1887400000 -1.2723190000 H 2.2050440000 -3.9568210000 -1.0662520000 H -4.0229530000 1.7227850000 -2.0268650000 H 1.0401420000 -3.1388040000 -2.1316560000 H -3.1303090000 0.2328360000 -2.3994200000 H 2.5953310000 -2.3669640000 -1.7550330000 C -3.3423020000 0.9859980000 1.8703210000 C -0.2599240000 -3.4212910000 1.4538730000 H -2.6629670000 1.1855230000 2.7059340000 H 0.3052320000 -3.7910660000 2.3173580000 H -4.1750780000 1.6963830000 1.9259730000 H -1.1793660000 -2.9493330000 1.8175750000 H -3.7437660000 -0.0261640000 1.9916270000 H -0.5403600000 -4.2795300000 0.8327740000 C -1.4221930000 3.0991330000 -0.1721770000 H -0.7124790000 3.2797160000 0.6430590000 H -0.8676530000 3.1757980000 -1.1142910000 (6c) biph_P_SnPh H -2.1835550000 3.8872820000 -0.1515870000 E = -893.1326799 Sn -2.3102380000 1.1809480000 0.0148920000 No. of Negative Frequencies = 0

(6b) biph_TS_SnPh E = -893.0977370 No. of Negative Frequencies = 1 freq = -402.6369

C 4.0070560000 -1.1956540000 0.1240490000 C 2.7944580000 -0.4740210000 0.1479470000 C 1.5696330000 -1.1681400000 0.3741220000 C 1.6184600000 -2.5540370000 0.6229060000 C 2.8289890000 -3.2556530000 0.6202390000 C 4.0294080000 -2.5741940000 0.3522030000 H 4.9405990000 -0.6630540000 -0.0309640000 C -4.1411010000 0.1544040000 -0.2589720000 H 0.6960100000 -3.0927780000 0.8254640000 C -2.7620120000 0.4300580000 -0.2545720000 H 2.8391820000 -4.3213860000 0.8226940000 C -1.8309520000 -0.6224660000 -0.4849380000 H 4.9717810000 -3.1118550000 0.3447630000 C -2.3348360000 -1.9082330000 -0.7676180000 C 3.6357220000 3.1079090000 -0.8304730000 C -3.7102050000 -2.1651350000 -0.8076810000 C 2.5370560000 3.8159330000 -0.2398340000 C -4.6206860000 -1.1323450000 -0.5338120000 C 1.5568660000 3.1568730000 0.4510980000 H -4.8368140000 0.9691450000 -0.0781510000 C 1.5941940000 1.6666200000 0.6815930000 H -1.6393490000 -2.7227180000 -0.9613140000 C 2.7503890000 0.9798100000 -0.0129820000 H -4.0683650000 -3.1625190000 -1.0402310000 C 3.7094720000 1.7054950000 -0.7068210000 H -5.6882090000 -1.3251850000 -0.5477460000 H 4.3926860000 3.6477170000 -1.3886970000 C -2.1152970000 3.8340630000 1.3254940000 H 2.4820760000 4.8947730000 -0.3519390000 C -1.1454140000 4.3540470000 0.4435810000 H 0.7353070000 3.7085650000 0.8984740000 C -0.7354010000 3.6144750000 -0.6672550000 H 1.7454200000 1.5166660000 1.7746950000 C -1.2514850000 2.3053400000 -0.8888300000 H 4.5213630000 1.1754990000 -1.1983460000 C -2.2636150000 1.8012120000 -0.0136000000 C -1.9750700000 1.5085360000 1.3573900000 C -2.6717260000 2.5641540000 1.0870560000 C -3.1848940000 2.2205820000 1.3221120000 H -2.4360710000 4.4142530000 2.1845710000 C -3.4275050000 3.1415960000 0.2923490000 H -0.7300030000 5.3417680000 0.6183660000 C -2.4511990000 3.3516670000 -0.6972810000 H -0.0110400000 4.0254480000 -1.3631870000 C -1.2436840000 2.6435900000 -0.6579070000 H -1.1591430000 1.8675070000 -1.8806260000 C -0.9955190000 1.7058360000 0.3648130000 H -3.4085560000 2.1539210000 1.7725540000 H -1.7782740000 0.8031400000 2.1609680000 C -0.3636590000 -0.4073510000 -0.3266060000 H -3.9300010000 2.0584900000 2.0946210000 C 0.2298340000 0.7821340000 -0.4470390000 H -4.3625030000 3.6913320000 0.2605980000 C 1.5663070000 1.3244290000 -0.4177530000 H -2.6352660000 4.0595190000 -1.4989410000 C 1.9467790000 2.2599950000 0.5738900000 H -0.4932700000 2.7982810000 -1.4280390000 C 2.5100490000 0.9522980000 -1.4076010000 C 0.2743820000 -0.4425730000 0.2769610000 C 3.2473820000 2.7744240000 0.5968550000 C 0.2680560000 0.9139050000 0.3975680000 H 1.2182430000 2.5575530000 1.3225570000 C -0.9578060000 -3.2812920000 -1.3377190000 C 3.8087040000 1.4747250000 -1.3801300000 H -0.9118830000 -4.1474400000 -0.6676040000 H 2.2094330000 0.2576040000 -2.1876370000 H -1.6959980000 -3.4935090000 -2.1204970000 C 4.1850960000 2.3825570000 -0.3754310000 H 0.0236440000 -3.1651970000 -1.8111070000 H 3.5338870000 3.4775720000 1.3723910000 C -2.6449560000 -2.0405240000 1.4401240000 H 4.5261640000 1.1752400000 -2.1375990000 H -3.3380930000 -1.2344060000 1.7067980000 H 5.1930470000 2.7836450000 -0.3533080000 H -3.2285150000 -2.9494250000 1.2539440000 Sn 0.9158770000 -2.0230610000 0.3502430000 H -1.9825490000 -2.2241580000 2.2940960000 C 2.4239580000 -1.2040640000 1.6043140000 C -2.6941960000 -0.3334830000 -1.6229150000 H 3.1703330000 -0.6559180000 1.0187610000 H -3.2410270000 0.4509800000 -1.0881440000 147 H -2.0583060000 0.1473700000 -2.3747170000 H -0.8510570000 -3.8003100000 1.5768650000 H -3.4167820000 -0.9760350000 -2.1405000000 H -1.3769410000 -2.8188260000 2.9801460000 Sn -1.5174300000 -1.5033160000 -0.2930970000 H -0.7689940000 -2.9874010000 -0.8465350000 H 0.8555240000 -4.1235060000 -2.3714930000

(7a) nap_SM E = -969.4944730 (7b) nap_TS_cis No. of Negative Frequencies = 1 E = -969.4774531 freq = -54.0225 No. of Negative Frequencies = 1 freq = -460.3317

C 0.9578870000 -2.1644030000 0.3332420000

C 0.7253840000 -1.8975720000 0.2153490000 C 2.1872280000 -1.4550530000 0.4356340000 C 2.1235480000 -1.5940280000 0.3415910000 C 2.2965430000 -0.2985410000 1.3031360000 C 2.6313740000 -0.6589590000 1.2984020000 C 4.4443850000 -0.9772070000 -0.4343290000 C 4.4431410000 -1.9356040000 -0.4348610000 C 4.5325120000 0.1380990000 0.3907930000 C 4.9032400000 -1.0287030000 0.4999260000 C 3.4847270000 0.4627020000 1.2821760000 C 3.9836940000 -0.3836790000 1.3755110000 C -0.2238410000 -1.5544870000 1.0559900000 C -0.2928840000 -1.1732540000 1.0816370000 C -0.4555980000 -0.1282060000 0.5292080000 C -0.6330170000 0.2005070000 0.4881210000 C 0.5203150000 0.7649860000 0.5224490000 C 0.1943330000 1.2041860000 0.3791740000 C 0.8081810000 2.1481010000 0.2435530000 C 0.9968380000 2.3142570000 0.1335640000 C 0.1946200000 3.1808130000 0.9936410000 C 1.0705140000 3.4145720000 1.0476290000 C 0.4999140000 4.5218500000 0.7350360000 C 1.9042850000 4.4995790000 0.7818640000 C 1.4276830000 4.8562330000 -0.2661510000 C 2.6913780000 4.5352290000 -0.3872310000 C 2.0575450000 3.8366470000 -1.0013270000 C 2.6325160000 3.4579160000 -1.2949810000 C 1.7614290000 2.4935140000 -0.7441080000 C 1.8069100000 2.3640270000 -1.0488330000 H -0.5225920000 2.9166820000 1.7659960000 H 0.4632870000 3.3910010000 1.9472830000 H 2.7793050000 4.0902270000 -1.7712300000 H 3.2400800000 3.4769050000 -2.1943520000 H 2.2528790000 1.7000470000 -1.3004350000 H 1.7725010000 1.5259960000 -1.7382610000 H 0.0137200000 5.3059040000 1.3068400000 H 1.9450920000 5.3270820000 1.4833480000 H 1.6604630000 5.8968150000 -0.4677860000 H 3.3377130000 5.3833860000 -0.5861420000 C 3.1254000000 -2.9134140000 -1.3014010000 C 2.5707900000 -3.1591030000 -1.5185190000 C 0.8294320000 -3.2247730000 -0.5532410000 C 0.2943710000 -2.7869480000 -0.7533530000 C 1.9358840000 -3.6226490000 -1.3503520000 C 1.2210370000 -3.4275390000 -1.6236300000 C 3.2668800000 -1.7924420000 -0.4311630000 C 3.0513510000 -2.2363070000 -0.5400180000 H 5.2648010000 -1.2428010000 -1.0950860000 H 5.1347170000 -2.4315100000 -1.1107120000 H 3.9565730000 -3.1850190000 -1.9463900000 H 3.2860040000 -3.6387060000 -2.1812550000 H 1.6735300000 -0.2366940000 2.1924650000 H 1.9506700000 -0.1401420000 1.9654230000 Sn -2.4110560000 0.1611680000 -0.3288930000 Sn -2.6658080000 0.3312830000 -0.2462730000 C -2.7031890000 -1.1781180000 -1.9545160000 C -2.6984280000 2.2590410000 -1.1583510000 H -2.8442700000 -2.1895710000 -1.5620380000 H -1.9711510000 2.3077430000 -1.9772790000 H -3.5783930000 -0.8935630000 -2.5499020000 H -3.6898710000 2.4947520000 -1.5627400000 H -1.8240180000 -1.1811940000 -2.6083280000 H -2.4302660000 3.0323950000 -0.4285590000 C -2.4365170000 2.1658550000 -1.0613350000 C -4.0668040000 0.2678400000 1.3528640000 H -3.3105140000 2.3227140000 -1.7056450000 H -5.0628590000 0.5799810000 1.0190330000 H -2.4778370000 2.8901120000 -0.2401040000 H -4.1239850000 -0.7532560000 1.7430200000 H -1.5335300000 2.3792740000 -1.6456450000 H -3.7520190000 0.9324940000 2.1647930000 C -3.9065350000 -0.0632280000 1.1708660000 C -3.0597850000 -1.1669510000 -1.7063880000 H -3.6510210000 0.5216580000 2.0617860000 H -3.2300740000 -2.1244510000 -1.2030080000 H -4.8843400000 0.2734640000 0.8081670000 H -3.9445870000 -0.9132130000 -2.3014510000 H -3.9767200000 -1.1183440000 1.4549450000 H -2.2069760000 -1.2750700000 -2.3860090000 H 3.5938120000 1.3017490000 1.9614210000 H 4.3495650000 0.3361770000 2.0999940000 H 5.4283350000 0.7510310000 0.3786130000 H 5.9616330000 -0.8004720000 0.5697170000 O -1.4566570000 -2.2779410000 0.8295120000 O -1.5658080000 -1.8737880000 1.1150440000 H -0.0375310000 -1.5140780000 2.1423970000 H 0.0740330000 -1.0690190000 2.1128440000 C -1.6569960000 -3.4179780000 1.6998360000 C -1.5862030000 -3.0686410000 1.9323340000 H -1.7497250000 -3.0907500000 2.7435040000 H -2.5906670000 -3.4850660000 1.8477920000 H -2.5850400000 -3.8941180000 1.3812200000 148 H -0.8273370000 -4.1304150000 1.6147820000 H 1.5041310000 -3.7073050000 -0.5981120000 H -0.1323370000 -3.7145950000 -0.6683400000 H 3.5698340000 -3.6104290000 -1.9960190000 H 1.8305310000 -4.4631920000 -2.0284770000

(7c) nap_P_cis (7b-t) nap_TS_trans E = -969.5184863 E = -969.4692633 No. of Negative Frequencies = 0 No. of Negative Frequencies = 1 freq = -419.5948

C 3.3064340000 -2.7651860000 -1.3688680000 C 2.1418210000 -2.8280950000 -0.5564560000 C -2.3634750000 -1.1655110000 -0.3497210000 C 4.0738030000 -1.6134990000 -1.3893350000 C -2.7396300000 0.1808530000 -0.3152890000 C 1.7975290000 -1.7667650000 0.2673200000 C -1.7242090000 1.2904010000 -0.5507550000 C 2.6228010000 -0.6067910000 0.3207270000 C -4.4789430000 1.9026350000 0.1041890000 C 3.7345770000 -0.4996450000 -0.5638180000 C -3.4788470000 2.8839960000 0.2953470000 C 4.4662420000 0.7300770000 -0.6224510000 C -2.1447740000 2.5999100000 0.0823850000 H 5.3145940000 0.8043230000 -1.2973230000 C -0.9047890000 -1.5687020000 -0.4681990000 C 4.0954410000 1.8091390000 0.1699170000 C 0.0937670000 -0.4440080000 -0.2508350000 C 3.0243500000 1.6961220000 1.0886800000 C -0.2855430000 0.8537100000 -0.2467670000 C 2.2705720000 0.5095400000 1.1728130000 C 0.7112650000 1.9420660000 -0.0144990000 H 4.9363430000 -1.5367080000 -2.0459460000 C 0.9764570000 2.9055580000 -1.0061770000 H 4.6554880000 2.7376270000 0.1171900000 C 1.9352180000 3.9046380000 -0.7911530000 H 2.7933380000 2.5243410000 1.7508190000 C 2.6305550000 3.9644320000 0.4284770000 H 1.7010650000 0.3005070000 2.0728960000 C 2.3574260000 3.0215280000 1.4306050000 C 0.4521020000 -1.7277540000 0.9498730000 C 1.4027060000 2.0166780000 1.2085540000 H -0.0940100000 -2.6563380000 0.7168810000 H 0.4443740000 2.8589620000 -1.9531960000 C -0.6080880000 -1.7152610000 3.1279340000 H 2.8829090000 3.0679470000 2.3790650000 H -1.2052390000 -2.5913460000 2.8313600000 H 1.1760280000 1.2928320000 1.9873320000 H -0.3435880000 -1.7963390000 4.1825120000 H 2.1425800000 4.6313130000 -1.5700830000 H -1.2001590000 -0.8053260000 2.9611810000 H 3.3722340000 4.7387850000 0.5949830000 O 0.6363750000 -1.6719480000 2.3931100000 C -5.0754390000 -0.5055570000 -0.0426390000 C -0.3538070000 -0.5100350000 0.4275260000 C -3.3377410000 -2.1783440000 -0.2570580000 C 0.1701500000 0.7097730000 0.4572970000 C -4.6935930000 -1.8477500000 -0.1259400000 C -0.1991350000 2.0789110000 0.2017310000 C -4.1092630000 0.5238730000 -0.1149930000 C -1.2498740000 2.6927840000 0.9278200000 H -5.5278040000 2.1477480000 0.2419650000 C 0.5114260000 2.8435310000 -0.7540450000 H -6.1192220000 -0.2393790000 0.0997270000 C -1.5999860000 4.0248180000 0.6771470000 H -1.7409010000 1.4817300000 -1.6464080000 H -1.7773480000 2.1159590000 1.6836760000 Sn 2.1129240000 -1.1765450000 -0.1805690000 C 0.1502600000 4.1713730000 -1.0047380000 C 2.7027340000 -1.6905050000 1.8027260000 H 1.3334160000 2.3795260000 -1.2918960000 H 2.5364080000 -0.8639880000 2.5027500000 C -0.9062260000 4.7676440000 -0.2937630000 H 2.1338100000 -2.5615140000 2.1459890000 H -2.4106230000 4.4840550000 1.2341120000 H 3.7687900000 -1.9451150000 1.8232370000 H 0.6920980000 4.7441780000 -1.7503390000 C 3.4627760000 0.2450950000 -1.0167470000 H -1.1798800000 5.7994790000 -0.4884560000 H 4.4236540000 -0.2369470000 -1.2353150000 Sn -2.2625360000 -0.8312190000 -0.5006910000 H 3.0585400000 0.6452320000 -1.9540930000 C -2.1467510000 -2.7616840000 -1.4027560000 H 3.6402260000 1.0872940000 -0.3387950000 H -2.9524060000 -2.9016610000 -2.1323090000 C 2.1181640000 -2.9131970000 -1.4120710000 H -1.1891770000 -2.8790300000 -1.9235930000 H 3.1040600000 -3.3924240000 -1.4075660000 H -2.2298610000 -3.5535590000 -0.6491720000 H 1.3777310000 -3.6244160000 -1.0313560000 C -3.7879370000 -0.8286740000 0.9919740000 H 1.8685750000 -2.6622130000 -2.4498980000 H -4.7759840000 -0.9613370000 0.5365600000 H -1.3835300000 3.3504730000 0.2682910000 H -3.6306890000 -1.6416630000 1.7099540000 H -3.7665450000 3.8733260000 0.6378210000 H -3.7882070000 0.1203920000 1.5401830000 O -0.5886120000 -2.6705680000 0.4535010000 C -2.5912490000 0.6967330000 -1.9377700000 H -0.7286930000 -2.0313010000 -1.4483410000 H -3.4685300000 0.4714430000 -2.5550220000 C -0.8140210000 -2.3661190000 1.8552420000 H -2.7471350000 1.6634060000 -1.4465500000 H -1.8780360000 -2.1969240000 2.0566890000 H -1.7184270000 0.7900090000 -2.5934910000 H -0.4665330000 -3.2380260000 2.4112330000 149 H -0.2446650000 -1.4785520000 2.1634870000 H -3.0148000000 -3.2151800000 -0.2763960000 (8a) 1anth_SM H -5.4412790000 -2.6319420000 -0.0687580000 E = -1123.054101 No. of Negative Frequencies = 0

(7c-t) nap_P_trans E = -969.5144225 No. of Negative Frequencies = 0

C -4.6201030000 -1.4786100000 1.0617440000 C -3.3354260000 -1.9398770000 0.7267610000 C -4.9387350000 -0.1314570000 0.8858660000 C -0.8888920000 0.5558940000 -2.1230230000 C -2.3861190000 -1.0564610000 0.1889250000 C -1.9346700000 0.3699880000 -1.1369840000 C -2.7020180000 0.2950830000 -0.0035950000 C -1.7635090000 0.6761740000 0.2254120000 C -3.9842710000 0.7795570000 0.3680000000 C -4.2388000000 -0.3504500000 -0.6410340000 C -4.2739570000 2.1906950000 0.2790670000 C -4.0631820000 -0.0520360000 0.7195450000 H -5.2646980000 2.5435090000 0.5489710000 C -2.7962670000 0.4764680000 1.1587240000 C -3.2478300000 3.1047610000 -0.0498400000 C 0.4919730000 1.0404700000 -1.7278340000 C -1.9835440000 2.6805690000 -0.4079970000 C 1.2494280000 0.1129170000 -0.7798790000 C -1.6561170000 1.2199510000 -0.6089460000 C 1.1712580000 -1.1924770000 -0.7608940000 H -5.9204010000 0.2401360000 1.1667060000 C 1.3006790000 -2.5278000000 -0.3671580000 H -3.4537690000 4.1697300000 0.0000600000 C 2.3151130000 -3.3806280000 -0.9024960000 H -1.2079460000 3.4087500000 -0.6216540000 C 2.4097380000 -4.7095730000 -0.4908750000 H -1.6785480000 1.0325330000 -1.7034290000 C 1.5043640000 -5.2373030000 0.4514480000 C -1.0064100000 -1.5395610000 -0.1952000000 C 0.4931010000 -4.4108840000 0.9806110000 H -0.7895730000 -2.4739820000 0.3490880000 C 0.3826380000 -3.0796310000 0.5831030000 C -1.7489550000 -2.9536040000 -2.0468990000 H 1.0848210000 1.1714790000 -2.6479850000 H -2.8150170000 -2.7134150000 -1.9537890000 H 3.0134670000 -2.9747360000 -1.6276410000 H -1.5050950000 -3.1476240000 -3.0920990000 H -0.2092850000 -4.8129820000 1.7039610000 H -1.5278500000 -3.8480780000 -1.4450580000 H -0.4019890000 -2.4423690000 0.9807450000 O -0.9191440000 -1.8407350000 -1.6333480000 H 3.1904040000 -5.3429340000 -0.9003530000 C 0.0738370000 -0.4971910000 0.0378640000 H 1.5839260000 -6.2725860000 0.7653850000 C -0.2327990000 0.8018540000 -0.1854890000 C -3.4050650000 -0.4609960000 -2.9668010000 C 0.8298590000 1.8483240000 -0.1264020000 C -1.1298810000 0.2490950000 -3.4424070000 C 1.1870370000 2.5790920000 -1.2770030000 C -2.3966790000 -0.2664800000 -3.8758200000 C 1.5328230000 2.0770590000 1.0704930000 C -3.2092550000 -0.1509840000 -1.5755250000 C 2.2420080000 3.4996380000 -1.2367060000 H -5.1933340000 -0.7455500000 -0.9825940000 H 0.6576920000 2.3987150000 -2.2092950000 H -4.3685730000 -0.8534310000 -3.2802210000 C 2.5890750000 3.0006620000 1.1137780000 O 0.4753300000 2.3207860000 -1.0210380000 H 1.2407320000 1.5336700000 1.9650780000 C -0.1232920000 3.4116690000 -1.7590260000 C 2.9499240000 3.7108410000 -0.0408970000 H 0.0298980000 4.3108980000 -1.1610860000 H 2.5190110000 4.0435220000 -2.1340330000 H 0.3628180000 3.5289000000 -2.7372780000 H 3.1233610000 3.1657150000 2.0440630000 H -1.1961710000 3.2408370000 -1.9053640000 H 3.7691900000 4.4216890000 -0.0110210000 H -0.8175120000 1.0842740000 0.5675520000 Sn 2.0666080000 -1.2432320000 0.2445910000 C -2.6236750000 0.7893710000 2.5523070000 C 2.8169090000 -1.0146810000 2.2316050000 H -1.6699270000 1.1964090000 2.8773210000 H 2.0081650000 -1.0948620000 2.9669720000 C -5.1064530000 -0.2533630000 1.6891050000 H 3.5602500000 -1.7896830000 2.4521900000 H -6.0591060000 -0.6527880000 1.3517250000 H 3.2950990000 -0.0352170000 2.3463520000 C -4.9042080000 0.0535280000 3.0134120000 C 1.8875000000 -3.3237200000 -0.1911830000 H -5.6954370000 -0.1009010000 3.7397870000 H 1.4542190000 -3.8702320000 0.6550220000 C -3.6422970000 0.5845850000 3.4521590000 H 1.2388780000 -3.4552520000 -1.0655800000 H -3.5031240000 0.8233520000 4.5013360000 H 2.8659590000 -3.7642650000 -0.4138450000 H -0.3406250000 0.3900170000 -4.1765170000 C 3.3597280000 -0.2654970000 -1.1309350000 H -2.5451930000 -0.5014020000 -4.9242750000 H 4.3084830000 -0.8052840000 -1.2301930000 Sn 2.4988920000 1.1645160000 0.6389560000 H 2.8860620000 -0.2052350000 -2.1169540000 C 1.3255300000 2.0091620000 2.2019340000 H 3.5704930000 0.7555430000 -0.7894990000 H 0.5957860000 2.7078740000 1.7792630000 H -3.0704750000 -2.9827700000 0.8830800000 H 0.7958870000 1.2174770000 2.7451870000 H -5.3559620000 -2.1646830000 1.4680530000 H 1.9584140000 2.5477770000 2.9167800000 C 3.6938510000 2.6225200000 -0.3489490000 150 H 4.1016820000 2.2157230000 -1.2813450000 H 2.4922270000 3.5490300000 1.9292150000 H 3.0794900000 3.4953430000 -0.5917380000 H 1.9695550000 3.4915810000 -0.4295210000 H 4.5323460000 2.9397410000 0.2813240000 H 0.4982070000 4.9469210000 -1.8412010000 C 3.7321260000 -0.3755770000 1.4469360000 C -3.5433650000 -0.5107010000 1.5385380000 H 3.1152680000 -1.1908900000 1.8439480000 H -2.9266450000 -1.0437220000 2.2581860000 H 4.3804740000 -0.7967360000 0.6696140000 C -5.1168540000 0.8528940000 -0.3617250000 H 4.3663340000 0.0031510000 2.2570150000 H -5.7203620000 1.3836630000 -1.0932910000 C -4.8403260000 -0.9169750000 1.2915320000 H -5.2578820000 -1.7674010000 1.8200240000 (8b) 1anth_TS_cis C -5.6359390000 -0.2239510000 0.3264840000 E = -1123.044155 H -6.6535940000 -0.5520850000 0.1400020000 No. of Negative Frequencies = 1 freq = -447.8904 (8b-t) 1anth_TS_trans E = -1123.036438 No. of Negative Frequencies = 1 freq = -384.1817

C 0.3479370000 2.3349340000 0.3480900000 C -1.0554530000 2.0594340000 0.2983790000 C -1.6167370000 0.9796000000 1.0417720000 C -3.2211670000 2.3976670000 -0.8199440000 C -3.7703880000 1.2929530000 -0.1341690000 C -2.9717620000 0.5906340000 0.8335190000 C 1.2038530000 1.3326050000 1.0877560000 C 1.0539770000 -0.0585320000 0.4405310000 C -0.1172530000 -0.6350280000 0.2776100000 C 0.0013200000 -2.5065440000 0.1507600000 C -0.9156490000 -1.7621690000 -0.0723710000 C 1.3292220000 -1.9673280000 0.0952820000 C -0.9383110000 -2.9158070000 0.7552480000 C 1.6921780000 -0.8325520000 0.8727820000 C -1.8072750000 -3.9743230000 0.4728270000 C 3.5029350000 -1.8628810000 -1.0537270000 C -2.6768200000 -3.9048450000 -0.6300990000 C 3.8424520000 -0.6926810000 -0.3425300000 C -2.6684030000 -2.7629200000 -1.4520310000 C 2.9410190000 -0.1876090000 0.6578720000 C -1.8063650000 -1.6988380000 -1.1760750000 C -1.0777590000 -1.7207010000 0.8671980000 H -0.2697280000 -2.9624910000 1.6104350000 C -1.1864130000 -0.2982910000 0.2843200000 H -3.3453050000 -2.6990950000 -2.2977490000 C -0.1310850000 0.4849320000 0.1716110000 H -1.8150870000 -0.8049060000 -1.7936760000 C 0.3986700000 1.7841940000 -0.0776300000 H -1.8088530000 -4.8537240000 1.1092750000 C 0.1447370000 2.8460810000 0.8314860000 H -3.3536360000 -4.7256260000 -0.8433390000 C 0.7355850000 4.0991440000 0.6378800000 C -1.2887940000 3.8623280000 -1.3733430000 C 1.5944510000 4.3187480000 -0.4535690000 C 0.8944760000 3.3432040000 -0.4258470000 C 1.8603630000 3.2699100000 -1.3532710000 C 0.0575280000 4.1425000000 -1.2613500000 C 1.2786130000 2.0135290000 -1.1675720000 C -1.8777260000 2.7850400000 -0.6315710000 H -2.0333290000 -2.2546970000 0.7374960000 H -3.8401110000 2.9508420000 -1.5229700000 H -0.5071870000 2.6649180000 1.6820210000 H -1.9184400000 4.4347320000 -2.0490200000 H 2.5332510000 3.4307540000 -2.1892100000 H -1.1246350000 0.6167810000 1.9403540000 H 1.4996160000 1.1943720000 -1.8459840000 Sn 2.9133690000 -0.8804390000 -0.2769840000 H 0.5305340000 4.9042660000 1.3364470000 C 3.7153380000 0.3581010000 -1.8070650000 H 2.0552210000 5.2905630000 -0.5975110000 H 4.5633560000 -0.1259130000 -2.3048700000 C 1.8886730000 -3.6735940000 -1.6036570000 H 2.9495500000 0.5759760000 -2.5596070000 C -0.3286790000 -3.6175960000 -0.6032720000 H 4.0469590000 1.3032350000 -1.3665100000 C 0.6358140000 -4.2304640000 -1.4622100000 C 2.3519950000 -2.7719410000 -1.0881770000 C 2.2631810000 -2.5058070000 -0.8566060000 H 3.2035760000 -3.2577410000 -1.5794730000 H 4.2054980000 -2.2716260000 -1.7768810000 H 1.9798410000 -3.4399710000 -0.3026930000 H 2.6079690000 -4.0999780000 -2.2977480000 H 1.5501610000 -2.6513350000 -1.8263460000 O -0.8470790000 -1.5616940000 2.2993410000 C 4.2851450000 -1.1722080000 1.3245280000 C -0.7582710000 -2.8244960000 3.0054470000 H 4.6617410000 -0.2009110000 1.6608100000 H -0.7079780000 -2.5800250000 4.0668740000 H 3.7938560000 -1.6672190000 2.1697370000 H -1.6457890000 -3.4434530000 2.8100930000 H 5.1321190000 -1.7923390000 1.0094660000 H 0.1381430000 -3.3812540000 2.7063180000 O 2.6154990000 1.6496330000 1.0235440000 H 1.1240460000 -0.5985920000 1.7678220000 H 0.9065220000 1.2689800000 2.1476450000 Sn -3.0955010000 0.4837040000 -0.3135050000 C 3.0622100000 2.6151730000 2.0067250000 C -4.2947790000 -1.1879600000 -0.8785800000 H 2.9559520000 2.2059450000 3.0194070000 H -4.5892590000 -1.7695370000 0.0025770000 H 4.1150010000 2.8087060000 1.7979380000 H -5.2072910000 -0.8574790000 -1.3875570000 151 H -3.7423160000 -1.8449770000 -1.5603320000 C 5.0547640000 1.5151520000 0.5643930000 C -2.7598900000 1.8243420000 -1.9258090000 H 6.0957590000 1.2780990000 0.3608750000 H -3.6905400000 2.3133840000 -2.2345190000 C 4.7243760000 2.6069580000 1.3690800000 H -2.0441470000 2.5985360000 -1.6251670000 H 5.5045270000 3.2405570000 1.7778100000 H -2.3425720000 1.2938570000 -2.7884790000 C 3.3755840000 2.8665330000 1.6661380000 C -3.9725690000 1.4969870000 1.3417280000 H 3.1108050000 3.6961950000 2.3132740000 H -3.4613630000 2.4507560000 1.5137320000 H 0.7723320000 -4.4563210000 -0.6245980000 H -5.0336700000 1.7028000000 1.1610400000 H 3.1282260000 -4.9811060000 -1.2138200000 H -3.8837620000 0.8908240000 2.2496780000 Sn -2.8607590000 -0.3475900000 0.0233800000 C 5.0765430000 0.0039410000 -0.5703720000 C -3.4853700000 0.3077410000 1.9531120000 C 3.3081800000 0.9765800000 1.4006360000 H -2.7027130000 0.0881320000 2.6879730000 C 4.4993450000 1.6293160000 1.1541630000 H -3.6905300000 1.3841590000 1.9594500000 H 4.7604910000 2.5220630000 1.7124160000 H -4.3971500000 -0.2199450000 2.2554850000 C 5.3937000000 1.1349260000 0.1519320000 C -3.6372940000 -2.3106250000 -0.2912510000 H 6.3274320000 1.6564110000 -0.0331300000 H -3.3975240000 -2.6922130000 -1.2905990000 H 5.7577420000 -0.3772700000 -1.3265880000 H -3.2186150000 -2.9934030000 0.4579420000 H 2.6170500000 1.3524880000 2.1509260000 H -4.7281310000 -2.3102640000 -0.1818800000 H -1.3419920000 -4.0107720000 -0.5687970000 C -3.5780200000 0.9489050000 -1.5077620000 H 0.3606880000 -5.1127230000 -2.0307850000 H -3.2703670000 1.9835740000 -1.3178910000 H -3.1729250000 0.6451200000 -2.4798870000 H -4.6724500000 0.9142110000 -1.5639690000 (8c) 1anth_P_cis E = -1123.0846338 No. of Negative Frequencies = 0 (8c-t) 1anth_P_trans E = -1123.090832 No. of Negative Frequencies = 0

C 1.1144610000 -2.3314330000 -0.3910650000 C 2.0470900000 -1.3019450000 -0.5120270000 C 1.6577660000 0.1628430000 -0.5231530000 C 4.3844560000 -0.5450020000 -0.6445390000 C 4.0437360000 0.6758230000 0.0338130000 C 2.6686810000 0.9938700000 0.2733000000 C 0.5522490000 -2.5416640000 -0.0812080000 C -0.3159520000 -2.0330320000 0.0030090000 C 1.6669740000 -1.6939500000 -0.0812180000 C -0.7334270000 -0.5826500000 -0.1316510000 C 1.5433590000 -0.3875580000 0.6812590000 C 0.1718550000 0.4113180000 -0.3006060000 C 3.9200640000 -1.1140630000 -0.8923280000 C -0.3027670000 1.8256290000 -0.4408860000 C 3.8892110000 0.1429100000 -0.2038350000 C -0.0062300000 2.5774210000 -1.5924660000 C 2.7573780000 0.5164120000 0.5787200000 C -0.5112510000 3.8764310000 -1.7460390000 C -0.6828890000 -2.0447620000 0.6490960000 C -1.3098530000 4.4493590000 -0.7434180000 C -0.9241400000 -0.5734420000 0.3214370000 C -1.5912540000 3.7162210000 0.4201400000 C 0.1607090000 0.2394880000 0.3403730000 C -1.0888820000 2.4160700000 0.5680240000 C 0.0418290000 1.6946030000 0.0422510000 H -0.9783730000 -2.6770500000 -0.6019100000 C 0.6947220000 2.2542250000 -1.0725960000 H 0.5999210000 2.1410230000 -2.3814280000 C 0.5212500000 3.6065060000 -1.3913610000 H -2.1932450000 4.1553720000 1.2095400000 C -0.2961830000 4.4231010000 -0.5898780000 H -1.2783410000 1.8600450000 1.4830110000 C -0.9326810000 3.8783790000 0.5352440000 H -0.2856350000 4.4388320000 -2.6463650000 C -0.7630940000 2.5205120000 0.8484610000 H -1.7000400000 5.4545620000 -0.8640380000 H -1.5455380000 -2.6706720000 0.3728980000 C 3.7969150000 -2.9391270000 -1.0255190000 H 1.3276710000 1.6233150000 -1.6909770000 C 1.5113800000 -3.6599210000 -0.6584290000 H -1.5549860000 4.5052110000 1.1663880000 C 2.8413700000 -3.9580940000 -0.9938120000 H -1.2391660000 2.0965510000 1.7292010000 C 3.4188240000 -1.6002150000 -0.7641110000 H 1.0196140000 4.0242960000 -2.2599660000 H 5.4274600000 -0.7505640000 -0.8739860000 H -0.4279740000 5.4715680000 -0.8369170000 H 4.8381570000 -3.1658040000 -1.2376550000 C 2.8438590000 -3.2758420000 -1.5181220000 O -0.6071090000 -2.3376980000 1.4127680000 C 0.5822140000 -3.7582590000 -0.7748030000 C -0.5285880000 -3.7343250000 1.7811700000 C 1.7422890000 -4.1289440000 -1.4863190000 H -0.9684000000 -3.8118410000 2.7765200000 C 2.8258080000 -2.0345430000 -0.8232530000 H -1.1004230000 -4.3596640000 1.0778550000 H 4.7985800000 -1.3760610000 -1.4771000000 H 0.5105060000 -4.0804880000 1.8120560000 H 3.7284120000 -3.5458680000 -2.0886120000 H 1.8473510000 0.4785700000 -1.5701320000 O -0.5191490000 -2.1231710000 2.1044160000 C 2.3588620000 2.0661400000 1.1124240000 C -0.3498490000 -3.4766130000 2.5917720000 H 1.3272510000 2.3010150000 1.3380030000 H -0.3415310000 -3.4129250000 3.6804060000 152 H -1.1852160000 -4.1139370000 2.2664460000 C 3.2120270000 -0.7323500000 1.6007060000 H 0.5918670000 -3.9134250000 2.2372120000 H 4.3954410000 -1.0108080000 3.4036190000 H 1.4319120000 -0.6596250000 1.7448270000 H 5.1921370000 0.0897410000 1.3795570000 C 2.8040620000 1.7071240000 1.3172300000 O -0.0329120000 -2.1819820000 -0.9527930000 H 1.9548070000 1.9774220000 1.9385680000 C 0.8799950000 -3.1482000000 -1.5232310000 C 5.0057870000 1.0224510000 -0.2619460000 H 0.3793830000 -4.1157210000 -1.4691680000 H 5.8620920000 0.7389350000 -0.8683810000 H 1.0991220000 -2.9006640000 -2.5709670000 C 5.0183920000 2.2168100000 0.4536590000 H 1.8164780000 -3.1831300000 -0.9545070000 H 5.8791160000 2.8755470000 0.4007370000 H -0.0475100000 -1.8043400000 1.2777590000 C 3.9150430000 2.5585830000 1.2617650000 Sn -2.6296500000 -1.0982140000 -0.3961620000 H 3.9223470000 3.4780890000 1.8370360000 C -2.5881960000 -2.5506610000 1.1616540000 H -0.2900340000 -4.4071420000 -0.7688500000 H -1.8512170000 -3.3251490000 0.9240540000 H 1.7705810000 -5.0716770000 -2.0227170000 H -2.3217110000 -2.0890870000 2.1197660000 Sn -2.8833400000 0.0608490000 -0.2494440000 H -3.5727100000 -3.0202830000 1.2723830000 C -3.9247560000 1.0147080000 1.3501730000 C -3.0822440000 -1.9908860000 -2.2738950000 H -3.5577480000 0.6500080000 2.3161160000 H -2.9568340000 -1.2672590000 -3.0870300000 H -3.7797590000 2.1000980000 1.3071920000 H -2.4011710000 -2.8304020000 -2.4459540000 H -4.9990690000 0.8066850000 1.2882710000 H -4.1143710000 -2.3584620000 -2.2977500000 C -3.9176210000 -1.7398640000 -0.7484470000 C -4.0652030000 0.4048700000 0.0785540000 H -3.3479480000 -2.3357650000 -1.4716530000 H -3.7729040000 0.9432260000 0.9881950000 H -4.0929510000 -2.3522400000 0.1442080000 H -4.1381230000 1.1399380000 -0.7317430000 H -4.8917560000 -1.5082570000 -1.1947830000 H -5.0582100000 -0.0312960000 0.2395020000 C -2.7723930000 1.3453440000 -1.9415880000 H 0.3607730000 -2.5276180000 3.5830660000 H -2.3759670000 2.3258500000 -1.6507750000 H 2.5899650000 -2.1571160000 4.6638490000 H -2.1040290000 0.9208820000 -2.6990360000 C 2.5835530000 0.7658270000 -2.3687050000 H -3.7627070000 1.4861600000 -2.3901250000 H 1.6312270000 0.6885830000 -2.8788620000 C 5.0699040000 1.1166260000 -1.0905640000 H 6.0200250000 1.2509130000 -0.5808620000 (9a) 9anth_SM C 3.6027680000 1.4437270000 -2.9936300000 E = -1123.048143 H 3.4450820000 1.8657680000 -3.9809330000 No. of Negative Frequencies = 0 C 4.8748480000 1.6161710000 -2.3528770000 H 5.6667620000 2.1504560000 -2.8668550000

(9b) 9anth_TS_cis E = -1123.03093 No. of Negative Frequencies = 1 freq = -447.2605

C 1.7296640000 -0.5163520000 -0.3696860000 C 1.9375090000 -0.9569820000 0.9631470000 C 0.9154350000 -1.6217790000 1.7338480000 C 3.4243190000 -1.1865660000 2.9486800000 C 2.4252950000 -1.8191160000 3.6460370000 C 1.1492420000 -2.0323480000 3.0248070000 C 0.4019170000 -0.7900000000 -1.0621340000 C -0.7763580000 0.0161030000 -0.5186080000 C -0.7372910000 1.2786290000 -0.1750720000 C 1.71012 0.55440 0.74662 C -1.1313600000 2.5309750000 0.3114960000 C 1.25789 1.89034 0.82947 C -1.6434390000 3.5397110000 -0.5620700000 C 0.01474 2.22755 1.51109 C -2.0241530000 4.7835320000 -0.0599660000 C 1.38718 4.26291 0.08374 C -1.9034310000 5.0709290000 1.3138360000 C 0.18574 4.54245 0.70907 C -1.3915140000 4.0894840000 2.1857540000 C -0.48540 3.53752 1.45362 C -1.0067310000 2.8394750000 1.7023080000 C 0.74054 -0.44018 1.36770 H 0.4960150000 -0.5835200000 -2.1342180000 C -0.58348 -0.42357 0.57882 H -1.7342990000 3.3194330000 -1.6211010000 C -1.26667 0.69415 0.42758 H -1.2944110000 4.3065850000 3.2448130000 C -2.48339 1.28455 -0.05392 H -0.6045260000 2.0841100000 2.3706050000 C -3.73828 0.90598 0.48448 H -2.4182900000 5.5358670000 -0.7359160000 C -4.91503 1.51087 0.02971 H -2.2010180000 6.0410940000 1.6970800000 C -4.86245 2.50830 -0.95927 C 4.2287550000 -0.0685750000 0.8994090000 C -3.61982 2.90541 -1.48364 C 2.7481680000 0.1995190000 -1.0493930000 C -2.43846 2.30978 -1.02976 C 4.0233030000 0.4108540000 -0.4000610000 H -3.77397 0.13402 1.24863 H -3.57391 3.68145 -2.24098 153 H -1.47321 2.62223 -1.41862 C -4.6761200000 1.8221660000 0.2203460000 H -5.87196 1.20422 0.43997 C -4.6399900000 2.7634560000 -0.8231050000 H -5.77692 2.97372 -1.31223 C -3.4212880000 3.0487780000 -1.4646000000 C 3.13644 2.63322 -0.55019 C -2.2467520000 2.3977940000 -1.0736820000 C 2.86860 0.23253 -0.02223 H 1.1065920000 -1.6934700000 1.1250700000 C 3.61593 1.31412 -0.62584 H -3.5233950000 0.4402040000 1.4271740000 C 1.94684 2.93903 0.12198 H -3.3895910000 3.7803040000 -2.2656110000 H 1.92499 5.03643 -0.45727 H -1.2997050000 2.6196450000 -1.5571930000 H 3.68006 3.42487 -1.06140 H -5.6131470000 1.6064250000 0.7237050000 H -0.35854 1.59352 2.30913 H -5.5478800000 3.2739190000 -1.1273220000 Sn -1.13227 -2.32466 -0.27199 C 3.5345040000 1.9500100000 -0.9345090000 C 0.44107 -3.09314 -1.47914 C 3.0140870000 -0.2907250000 -0.0492920000 H 1.14499 -3.64768 -0.84963 C 3.8648780000 0.5889110000 -0.8168720000 H 0.05030 -3.76308 -2.25368 C 2.4201050000 2.4916790000 -0.2790190000 H 0.98704 -2.27752 -1.96633 H 2.6652220000 4.5008680000 -1.0820770000 C -2.83454 -1.91297 -1.48991 H 4.1498070000 2.5927880000 -1.5607490000 H -3.02540 -2.74492 -2.17854 O 0.5823330000 -0.3904970000 2.6416490000 H -3.73155 -1.75598 -0.88049 C 1.7666320000 -0.6072100000 3.4488930000 H -2.67293 -1.00353 -2.08101 H 1.4628820000 -0.4637090000 4.4861530000 C -1.66636 -3.67699 1.28291 H 2.1492230000 -1.6291770000 3.3144730000 H -2.41273 -3.22779 1.94783 H 2.5571830000 0.1076930000 3.1884070000 H -2.08467 -4.60377 0.87387 H 0.0569630000 1.6839140000 2.0921480000 H -0.77628 -3.92032 1.87242 Sn -1.5661960000 -2.1451450000 -0.3118900000 H -1.39147 3.78501 1.99683 C -0.0550420000 -3.6062200000 -0.6792520000 H -0.23304 5.54268 0.66486 H 0.3125380000 -4.0290070000 0.2636120000 C 3.33692 -1.10730 -0.27654 H -0.4469750000 -4.4288230000 -1.2882610000 H 2.74957 -1.94156 0.07810 H 0.7915920000 -3.1585060000 -1.2132630000 C 4.81999 1.02974 -1.35571 C -2.5435540000 -1.5260330000 -2.0927300000 H 5.37146 1.86519 -1.77887 H -3.0454880000 -2.3680470000 -2.5824070000 C 4.48588 -1.34210 -0.99998 H -3.2932040000 -0.7594290000 -1.8641650000 H 4.80532 -2.36371 -1.18007 H -1.8211610000 -1.0951310000 -2.7944290000 C 5.25639 -0.26110 -1.53266 C -2.9713430000 -2.8857400000 1.1090510000 H 6.16481 -0.46794 -2.08864 H -3.2253490000 -3.9313450000 0.9008840000 O 1.15516 -1.82418 1.42917 H -2.5559030000 -2.8225660000 2.1206020000 H 0.53364 -0.12508 2.40319 H -3.8933290000 -2.2944700000 1.0767700000 C 2.06425 -2.12040 2.51829 H -0.6804080000 3.9982850000 1.5933350000 H 1.58395 -1.90772 3.48171 H 0.6515600000 5.4212020000 0.0406050000 H 2.29787 -3.18367 2.45034 C 3.3845560000 -1.6817140000 0.0106400000 H 2.98701 -1.53353 2.42911 H 2.7884760000 -2.3789260000 0.5883370000 C 5.0222100000 0.0568190000 -1.4808290000 H 5.6447530000 0.7386590000 -2.0540190000 (9b-t) 9anth_TS_trans C 4.5043010000 -2.1572700000 -0.6355280000 E = -1123.027556 H 4.7630010000 -3.2088820000 -0.5653070000 No. of Negative Frequencies = 1 C 5.3385720000 -1.2778690000 -1.3978830000 freq = -385.4909 H 6.2152610000 -1.6714370000 -1.9011460000

(9c) 9anth_P_cis E = -1123.071816 No. of Negative Frequencies = 0

C 1.8727480000 0.2525050000 0.6044510000 C 1.6096830000 1.6358710000 0.5500500000 C 0.4670860000 2.2139450000 1.2395140000 C 2.0471640000 3.8708100000 -0.4483010000 C 0.9265270000 4.3801840000 0.1782960000 C 0.1525330000 3.5631340000 1.0505550000 C 0.8101080000 -0.6428200000 1.2204120000 C -0.5393180000 -0.4444020000 0.5057370000 C 3.6878620000 -1.7352940000 -0.6293870000 C -1.0778460000 0.7542710000 0.3631910000 C 3.3767900000 -0.3829450000 -0.2942790000 C -2.2784980000 1.4274830000 -0.0429160000 C 2.0213990000 0.0945850000 -0.1054540000 C -3.5073400000 1.1605650000 0.6133820000 C 4.1912190000 1.9158940000 0.0702990000 154 C 2.8832450000 2.3828240000 0.1707880000 C 3.5446240000 -1.8600110000 -0.2424820000 C 1.7900650000 1.4517070000 -0.0031870000 C 3.2364410000 -0.4664750000 -0.1766740000 C 0.8592840000 -0.8803450000 0.0017090000 C 1.9799630000 0.0491960000 0.3007870000 C -0.5245930000 -0.2777230000 -0.1544400000 C 3.9718090000 1.8583250000 -0.5441970000 C -0.7222250000 1.0566600000 -0.1760480000 C 2.7485920000 2.3493660000 -0.0844000000 C -2.1013560000 1.6326800000 -0.2262460000 C 1.7480230000 1.4107810000 0.3552030000 C -2.5356260000 2.3703170000 -1.3436220000 C 0.8545390000 -0.8558080000 0.7752090000 C -3.8427890000 2.8731180000 -1.4004290000 C -0.5099760000 -0.3535830000 0.3226580000 C -4.7284920000 2.6594470000 -0.3309780000 C -0.7321890000 0.9777120000 0.4029500000 C -4.2951260000 1.9478430000 0.7982440000 C -2.0729970000 1.5604570000 0.1045320000 C -2.9875610000 1.4407450000 0.8501880000 C -2.2673390000 2.4168950000 -0.9968190000 H 0.9872330000 -1.7062340000 -0.7159950000 C -3.5481120000 2.8902950000 -1.3107360000 H -1.8567840000 2.5275120000 -2.1777550000 C -4.6513790000 2.5249940000 -0.5193060000 H -4.9692790000 1.7894690000 1.6340340000 C -4.4632970000 1.6899610000 0.5916180000 H -2.6415130000 0.9024690000 1.7291290000 C -3.1801520000 1.2119630000 0.9013080000 H -4.1719170000 3.4244180000 -2.2754480000 H 1.0168640000 -1.8836980000 0.4284610000 H -5.7409000000 3.0472860000 -0.3764720000 H -1.4156040000 2.6911190000 -1.6131630000 C 5.8021120000 0.0987460000 -0.4135430000 H -5.3084470000 1.4119970000 1.2134210000 C 4.9935370000 -2.1447800000 -0.8433590000 H -3.0261480000 0.5730060000 1.7673150000 C 6.0686300000 -1.2211450000 -0.7205910000 H -3.6888010000 3.5358030000 -2.1717440000 C 4.4621290000 0.5509480000 -0.2142110000 H -5.6428380000 2.8910300000 -0.7654240000 H 5.0226800000 2.6035210000 0.2087850000 C 5.5022450000 -0.0175160000 -1.0673680000 H 6.6100730000 0.8206870000 -0.3301710000 C 4.7734040000 -2.3019770000 -0.7026300000 O 0.7487450000 -1.4766140000 1.3503040000 C 5.7665020000 -1.3713660000 -1.1217890000 C 1.7757340000 -2.3985430000 1.7862190000 C 4.2426430000 0.4671140000 -0.5965180000 H 1.4483290000 -2.7615440000 2.7618550000 H 4.7344190000 2.5560750000 -0.8838240000 H 1.8689270000 -3.2489040000 1.0958550000 H 6.2502470000 0.7043730000 -1.3842710000 H 2.7477820000 -1.9044500000 1.8852730000 O 0.7817920000 -0.8884460000 2.2445460000 C 0.4144580000 2.0612390000 -0.1989320000 C 1.9487500000 -1.4728110000 2.8742290000 H 0.4462840000 2.4512570000 -1.2414420000 H 1.7496130000 -1.4749530000 3.9464460000 C 2.5890610000 3.7409740000 0.5606780000 H 2.1036560000 -2.5047010000 2.5279210000 H 3.4175320000 4.4270070000 0.7117690000 H 2.8524610000 -0.8864540000 2.6663510000 C 1.2712790000 4.1236560000 0.9139540000 C 0.4078880000 1.8991710000 0.8871590000 H 1.1116820000 5.0764140000 1.4092640000 H 0.4262160000 1.7141840000 1.9798380000 C 0.1989060000 3.2957150000 0.6512750000 C 2.4554080000 3.7598010000 -0.0838250000 H -0.8117100000 3.5600970000 0.9465960000 H 3.2250050000 4.4533890000 -0.4093360000 H 5.2000610000 -3.1763590000 -1.1094330000 C 1.1741950000 4.2319680000 0.2823320000 H 7.0884390000 -1.5556230000 -0.8784990000 H 0.9699240000 5.2969710000 0.2280720000 Sn -2.0703040000 -1.7540050000 -0.0760300000 C 0.1758860000 3.3754500000 0.7004760000 C -2.8504590000 -1.9634530000 1.8953360000 H -0.7982370000 3.7648790000 0.9807960000 H -2.0995670000 -1.6100530000 2.6105000000 H 4.9844400000 -3.3655080000 -0.7450270000 H -3.7706980000 -1.3817700000 2.0215540000 H 6.7244790000 -1.7318080000 -1.4814210000 H -3.0717490000 -3.0140720000 2.1152560000 Sn -1.9579670000 -1.7841310000 -0.3211200000 C -1.1186500000 -3.5730260000 -0.6592910000 C -3.2803120000 -2.3208170000 1.2647560000 H -0.7000720000 -3.5011440000 -1.6701490000 H -2.7785490000 -2.1916940000 2.2304690000 H -0.3090210000 -3.8080120000 0.0420500000 H -4.1767910000 -1.6905720000 1.2484740000 H -1.8325210000 -4.4047630000 -0.6469020000 H -3.5923040000 -3.3675020000 1.1734550000 C -3.6195270000 -1.2851960000 -1.4621770000 C -0.8098910000 -3.5040860000 -0.8559150000 H -4.1963630000 -0.4191030000 -1.1165870000 H 0.0069250000 -3.2386690000 -1.5380900000 H -3.1934640000 -1.0400390000 -2.4419420000 H -0.3782030000 -3.9733080000 0.0366980000 H -4.3039700000 -2.1329030000 -1.5849820000 H -1.4402120000 -4.2483260000 -1.3561210000 H 2.8899240000 -2.4599020000 -0.7421680000 C -3.0515930000 -1.0482330000 -1.9902550000 H -3.6960040000 -0.2161920000 -1.6810600000 H -2.3704080000 -0.6806320000 -2.7657280000 (9c-t) 9anth_P_trans H -3.6798460000 -1.8349860000 -2.4236740000 E = -1123.077783 H 2.8100770000 -2.5943030000 0.0689530000 No. of Negative Frequencies = 0

(10a) 1panth_SM E = -1123.0634101 No. of Negative Frequencies = 0

155 C -5.8572760000 -1.4066680000 0.8401820000 H -6.0001290000 -2.6398160000 2.6230140000 H -6.9263000000 -1.2308580000 0.7805450000 C -5.0107350000 -0.8474550000 -0.1082410000 H -5.4434040000 -0.2399220000 -0.8943380000

(10b) 1panth_TS_cis E = -1123.047426 No. of Negative Frequencies = 1 freq = -457.7919

C -0.8012980000 -1.5428690000 0.1774080000 C -1.2842110000 -0.7074350000 -0.9021480000 C -0.3768060000 -0.0904330000 -1.8194010000 C -3.1449840000 0.3437900000 -2.0981520000 C -2.2574260000 0.9165280000 -2.9946520000 C -0.8675590000 0.6995940000 -2.8494950000 C 1.1268190000 -0.1531430000 -1.6193140000 C 0.2129680000 -2.1519030000 0.5001060000 C 1.5832750000 0.5326290000 -0.3210530000 C 1.4551980000 -1.4765660000 0.6287390000 C 0.9184080000 1.5195820000 0.2334890000 C 1.5443940000 -0.3000260000 1.4926420000 C -0.1357890000 2.4327280000 0.4357970000 C 3.7835040000 -1.0522350000 -0.1583000000 C -0.0424260000 3.7840370000 -0.0098640000 C 3.8310120000 0.1141910000 0.6649600000 C -1.0978550000 4.6725880000 0.1997210000 C 2.7270090000 0.4374430000 1.5199070000 C -2.2673750000 4.2520680000 0.8613860000 C -0.9873350000 -1.4946570000 1.1517090000 C -2.3684440000 2.9236300000 1.3172920000 C -1.1628700000 -0.0823830000 0.5722890000 C -1.3224960000 2.0223190000 1.1167400000 C -0.1679290000 0.7889780000 0.5963940000 H 1.6079820000 0.3498390000 -2.4738550000 C 0.1731680000 2.1572740000 0.3051180000 H 0.8602030000 4.1079000000 -0.5184910000 C -0.4848160000 3.2233380000 0.9655680000 H -3.2680210000 2.5910710000 1.8258310000 C -0.1221600000 4.5495760000 0.7048740000 H -1.4018490000 0.9963310000 1.4667900000 C 0.9082890000 4.8355290000 -0.2071210000 H -1.0148160000 5.6963920000 -0.1513610000 C 1.5800190000 3.7825630000 -0.8530430000 H -3.0837630000 4.9485270000 1.0211990000 C 1.2254940000 2.4542610000 -0.5937920000 C -3.6059040000 -1.0562700000 -0.0576370000 H -1.2790670000 2.9957470000 1.6711840000 C -1.6647200000 -2.0902780000 1.0813340000 H 2.3807970000 3.9975900000 -1.5532290000 C -2.6836040000 -0.4756150000 -1.0331350000 H 1.7471190000 1.6368000000 -1.0840660000 H -4.2041230000 0.5382350000 -2.2165650000 H -0.6411930000 5.3594960000 1.2077180000 O 1.6741560000 -1.5030660000 -1.5343010000 H 1.1868350000 5.8647810000 -0.4089930000 C 1.4159070000 -2.3298330000 -2.6935050000 C 2.4190170000 -3.0062420000 -1.0014930000 H 1.9590700000 -3.2622650000 -2.5361670000 C 0.0873290000 -3.2431740000 -0.3521850000 H 1.7774730000 -1.8385950000 -3.6073750000 C 1.2113340000 -3.6921080000 -1.0789540000 H 0.3438230000 -2.5366380000 -2.7936130000 C 2.5612460000 -1.8644810000 -0.1717160000 H 0.2627600000 -1.7344040000 0.2471500000 H 3.2499020000 -3.3437610000 -1.6100520000 H -1.2927680000 -2.7169490000 1.8876380000 H 0.8773460000 -0.2214020000 2.3473520000 Sn 3.3278530000 -0.3331560000 0.5900550000 Sn -3.0395910000 0.1939820000 -0.4512110000 C 2.8137610000 -2.1754950000 1.5230320000 C -3.1947040000 -1.2318180000 -2.0212270000 H 2.4944700000 -2.8900690000 0.7574190000 H -3.5408290000 -2.1842100000 -1.6082260000 H 1.9923610000 -2.0288890000 2.2344120000 H -3.8899570000 -0.8980550000 -2.7997990000 H 3.6674300000 -2.5946940000 2.0679430000 H -2.2111480000 -1.3935950000 -2.4765260000 C 4.8598480000 -0.5831160000 -0.8655520000 C -2.9620010000 2.1578960000 -1.2842110000 H 5.1010810000 0.3730830000 -1.3430790000 H -3.7363410000 2.2756380000 -2.0523020000 H 4.5146120000 -1.2821290000 -1.6344100000 H -3.1193590000 2.9237650000 -0.5164360000 H 5.7755800000 -0.9801400000 -0.4132220000 H -1.9851040000 2.3457970000 -1.7455620000 C 3.9194500000 1.0743280000 2.0763560000 C -4.6693790000 0.0731150000 0.9137080000 H 3.0479530000 1.3709570000 2.6720990000 H -4.7601710000 -0.9535350000 1.2828570000 H 4.3341390000 1.9771330000 1.6142450000 H -4.5081460000 0.7387310000 1.7692710000 H 4.6734200000 0.6534490000 2.7513480000 H -5.6093200000 0.3604000000 0.4287060000 H -0.1737940000 1.1752270000 -3.5378920000 H 2.8263190000 1.2792750000 2.1992980000 H -2.6247600000 1.5435800000 -3.7998130000 O -2.2229720000 -2.2001430000 0.8857190000 C -3.0861890000 -1.8574220000 0.9974180000 H -0.8529470000 -1.4281390000 2.2441100000 C -3.9657500000 -2.4240700000 1.9575390000 C -2.4889170000 -3.3101630000 1.7771700000 C -5.3330160000 -2.2054110000 1.8860050000 H -2.6226640000 -2.9508230000 2.8055750000 H -3.5461710000 -3.0338740000 2.7529000000 H -3.4116010000 -3.7756480000 1.4287360000 H -1.6720810000 -4.0418560000 1.7510650000 156 C 4.9173680000 -1.3647090000 -0.9475250000 C -4.4026990000 0.6209170000 1.0899840000 C 6.0530060000 -0.5596890000 -0.9357100000 H -5.4454930000 0.3099660000 0.9609720000 C 6.0951810000 0.5993750000 -0.1233780000 H -4.0450420000 0.2460140000 2.0553180000 C 5.0006260000 0.9249630000 0.6638730000 H -4.3695720000 1.7161860000 1.1065120000 H 6.9078100000 -0.8207590000 -1.5508610000 H -0.1185550000 -4.0073390000 -0.8968910000 H 6.9810760000 1.2258670000 -0.1184290000 H 2.4637820000 1.4762750000 2.1289520000 H 5.0179270000 1.8106060000 1.2932070000 C 5.1307810000 -0.5731040000 -1.0260990000 H 4.9125470000 -2.2448020000 -1.5807070000 C 6.0968350000 0.4235820000 -0.9218500000 H 1.1211440000 -4.5535510000 -1.7324990000 C 4.7236840000 1.6058840000 0.6858160000 H -0.8818920000 -3.7124140000 -0.4870070000 C 5.8919050000 1.5259990000 -0.0575350000 H 4.5518750000 2.4441480000 1.3554010000 H 6.6471500000 2.3010950000 0.0212960000 (10b-t) 1panth_TS_trans H 7.0091840000 0.3562790000 -1.5052970000 E = -1123.039853 H 5.3137060000 -1.4034290000 -1.6989270000 No. of Negative Frequencies = 1 H 3.9018990000 -2.8115500000 -1.8179840000 freq = -406.2135 H 2.0541260000 -4.4084120000 -2.0634500000

(10c) 1panth_P_cis E = -1123.086174 No. of Negative Frequencies = 0

C 0.5843310000 -2.2598400000 0.1383350000 C 1.6800600000 -1.3819880000 0.3623770000 C 1.5275330000 -0.2691210000 1.2945830000

C 3.9269520000 -0.5139600000 -0.2809050000 C 0.5809110000 -2.1764450000 0.2921340000 C 3.7246010000 0.5978920000 0.5916050000 C 1.6567750000 -1.2782060000 0.3901530000 C 2.5455300000 0.6690900000 1.4062250000 C 1.3701900000 0.0473970000 1.0809980000 C -0.7797940000 -1.9029660000 0.7022870000 C 4.0300090000 -0.6306790000 -0.0806810000 C -1.1963680000 -0.4903190000 0.2642660000 C 3.7794560000 0.6696340000 0.4768820000 C -0.3564810000 0.5295320000 0.3756160000 C 2.5089260000 1.0147550000 0.9930150000 C -0.3121990000 1.9636080000 0.2397480000 C -0.7278730000 -1.7144940000 0.9059900000 C -1.1885060000 2.7885920000 0.9869860000 C -1.0309120000 -0.2775180000 0.4978480000 C -1.1309120000 4.1815210000 0.8552870000 C -0.0034390000 0.5952560000 0.5950350000 C -0.1945730000 4.7723860000 -0.0102630000 C -0.1253230000 2.0504640000 0.2967740000 C 0.6959460000 3.9606450000 -0.7353200000 C 0.5414960000 2.6165190000 -0.8078180000 C 0.6479350000 2.5686750000 -0.6049350000 C 0.4126580000 3.9826060000 -1.0916750000 H -1.5046050000 -2.6446550000 0.3297450000 C -0.3711500000 4.8051200000 -0.2637070000 H -1.8980660000 2.3259270000 1.6684950000 C -1.0245500000 4.2520230000 0.8469430000 H 1.4276660000 4.4133230000 -1.3966290000 C -0.9022490000 2.8813540000 1.1231830000 H 1.3391910000 1.9351720000 -1.1537250000 H 1.1487620000 1.9789110000 -1.4450610000 H -1.8105630000 4.8058100000 1.4265620000 H -1.6321650000 4.8811820000 1.4897120000 H -0.1527880000 5.8520140000 -0.1117990000 H -1.4115710000 2.4456960000 1.9787470000 C 2.9913840000 -2.6536230000 -1.2514170000 H 0.9184360000 4.4049710000 -1.9539910000 C 0.7230870000 -3.3407050000 -0.7250200000 H -0.4701930000 5.8631950000 -0.4836170000 C 1.9449120000 -3.5561240000 -1.4010510000 C 3.0451120000 -2.8406720000 -0.8279850000 C 2.8761710000 -1.5328950000 -0.3873790000 C 0.7206440000 -3.3917110000 -0.3805510000 O -0.8398470000 -1.9194560000 2.1618660000 C 1.9676600000 -3.7228180000 -0.9363930000 C -0.5118120000 -3.2109010000 2.7321840000 C 2.9114480000 -1.5975200000 -0.1675790000 H -0.6830590000 -3.1252130000 3.8055760000 H 3.9892380000 -3.1159840000 -1.2837270000 H -1.1590270000 -3.9961890000 2.3157850000 H 1.2061970000 -0.1764180000 2.1570060000 H 0.5360670000 -3.4720560000 2.5400720000 Sn -2.9939690000 -0.0353700000 -0.3302860000 H 0.7967590000 -0.3694120000 2.0911580000 C -3.0997580000 -1.1389980000 -2.1451220000 Sn -3.1779540000 -0.1344710000 -0.4839160000 H -2.8565260000 -2.1856000000 -1.9400420000 C -3.9246160000 -2.0195310000 -1.1471920000 H -4.1035450000 -1.0782230000 -2.5817380000 H -4.0870970000 -2.6944190000 -0.2988950000 H -2.3826180000 -0.7476990000 -2.8753910000 H -4.8815590000 -1.8919440000 -1.6660970000 C -3.4118400000 2.0046960000 -0.7997020000 H -3.2218910000 -2.4951930000 -1.8411530000 H -4.2986990000 2.0466550000 -1.4451910000 C -3.0463680000 1.2698200000 -2.0731290000 H -3.6108820000 2.5935500000 0.1021040000 H -4.0282890000 1.4460950000 -2.5266850000 H -2.5743740000 2.4745910000 -1.3290620000 H -2.6598900000 2.2243620000 -1.6976010000 C -4.4371800000 -0.7083780000 1.0890210000 H -2.3633580000 0.9079180000 -2.8490670000 H -4.1001110000 -0.5045250000 2.1125620000 157 H -5.4034640000 -0.2128660000 0.9415310000 H -4.3881250000 1.1986830000 1.3851170000 H -4.5750190000 -1.7896780000 0.9800020000 H -5.2905240000 -0.3156750000 1.1512830000 H 2.3625710000 2.0088110000 1.4071050000 C -3.6504320000 -2.2559670000 -1.1673560000 O -1.8467290000 -2.5462080000 0.5128260000 H -2.9644220000 -2.6035140000 -1.9487120000 H -0.6309110000 -1.7483360000 2.0092570000 H -3.6797290000 -3.0090840000 -0.3708000000 C -2.1597720000 -3.6228030000 1.4292330000 H -4.6536530000 -2.1873850000 -1.6040420000 H -2.5148250000 -3.2207530000 2.3869980000 C -3.2125550000 1.1485520000 -1.8872450000 H -2.9530730000 -4.2081090000 0.9624490000 H -3.0689610000 2.1395340000 -1.4393710000 H -1.2844200000 -4.2612990000 1.6041120000 H -2.4454080000 1.0103460000 -2.6572830000 C 5.3239520000 -0.9301810000 -0.5373490000 H -4.1975190000 1.1200420000 -2.3675000000 C 6.3596090000 0.0114140000 -0.4792410000 H 2.9801000000 -4.3428570000 -1.7313880000 C 6.1129110000 1.2995810000 0.0447390000 H 0.6286750000 -4.1478090000 -0.8963150000 C 4.8459330000 1.6203640000 0.5140130000 C 3.5917450000 1.1619790000 0.3547320000 H 7.3494010000 -0.2502750000 -0.8375880000 C 4.4784870000 2.2768020000 0.4700980000 H 6.9124830000 2.0320210000 0.0851120000 C 5.4595960000 -0.1549410000 -0.5117260000 H 4.6452130000 2.6057840000 0.9258700000 C 5.8161810000 2.1721980000 0.1126230000 H 5.5425360000 -1.9115270000 -0.9433420000 H 4.0837470000 3.2126230000 0.8566190000 H 2.0926980000 -4.6618120000 -1.4654400000 C 6.3169270000 0.9443680000 -0.3745080000 H -0.1347450000 -4.0486300000 -0.4956100000 H 6.4775710000 3.0265680000 0.2127410000 H 7.3636650000 0.8515920000 -0.6435150000 H 1.1926140000 -0.1676700000 1.8924090000 (10c-t) 1panth_P_trans H 5.8719330000 -1.0852440000 -0.8865760000 E = -1123.083974 C -0.6048250000 3.9813730000 -0.8764070000 No. of Negative Frequencies = 0 H -0.2368590000 4.6140150000 -1.6776250000

(11a) 9panth_SM E = -1123.063552 No. of Negative Frequencies = 0

C 1.3050600000 0.1186500000 0.8264430000 C 1.8347490000 -1.1131770000 0.1114280000

C 0.9331030000 -2.1734270000 -0.0850230000 C 1.1896940000 -0.5771240000 0.9296060000 C 3.5529410000 -2.3929450000 -1.0200630000 C 1.9388590000 0.6612780000 1.0717920000 C 2.6570240000 -3.4466210000 -1.2122920000 C 1.4161620000 1.7619610000 1.8053080000 C 1.3374800000 -3.3375180000 -0.7447930000 C 3.9267990000 2.0081950000 0.6005690000 C -0.4800330000 -2.0110230000 0.4367500000 C 3.3964440000 3.0701620000 1.3204050000 C -1.0113860000 -0.6073410000 0.1896250000 C 2.1265350000 2.9466770000 1.9293480000 C -0.1501010000 0.4164370000 0.3935820000 C -0.2111190000 -0.6838680000 1.5117280000 C -0.5988350000 1.8361070000 0.2835740000 C -1.2365130000 -0.0391250000 0.5698200000 C -0.1139640000 2.6763680000 -0.7376710000 C -1.3127890000 1.2308110000 0.2777400000 C -1.5788160000 4.4691220000 0.0126130000 C -1.4776180000 2.5248320000 -0.2086890000 C -2.0514790000 3.6460850000 1.0451510000 C -0.6883930000 2.9750990000 -1.3180980000 C -1.5624240000 2.3367800000 1.1792210000 C -0.8277040000 4.2726480000 -1.8045630000 H -1.1224920000 -2.7769520000 -0.0263280000 C -1.7430230000 5.1687120000 -1.2149630000 H 0.6300800000 2.2947530000 -1.4315780000 C -2.5213470000 4.7431790000 -0.1194550000 H -2.7951160000 4.0192530000 1.7422800000 C -2.3976330000 3.4488360000 0.3835560000 H -1.9180160000 1.6971210000 1.9829800000 H -0.2578930000 -0.2274080000 2.5106800000 H -1.9601280000 5.4790470000 -0.0977900000 H 0.0252450000 2.2870880000 -1.7612180000 C 4.0995250000 -0.0748740000 -0.1703170000 H -3.2277460000 5.4296090000 0.3371890000 C 2.2445310000 1.2827970000 0.7670870000 H -2.9992360000 3.1234870000 1.2266320000 C 3.1637400000 -1.2087540000 -0.3523860000 H -0.2221840000 4.5955760000 -2.6456160000 H 4.5590360000 -2.4899660000 -1.4115390000 H -1.8465530000 6.1772830000 -1.6004540000 O -0.5392760000 -2.2001490000 1.8926910000 C 3.7655000000 -0.3319600000 -0.3146840000 C -0.1602210000 -3.5308140000 2.3216400000 C 1.7058700000 -1.6095880000 0.1993690000 H -0.3767960000 -3.5826590000 3.3892250000 C 3.2196160000 0.7859600000 0.4544020000 H -0.7470710000 -4.2940520000 1.7893540000 H 4.9008800000 2.1268860000 0.1406060000 H 0.9067320000 -3.7176160000 2.1493680000 O -0.6423130000 -2.0668720000 1.6191790000 H 1.8993870000 2.2344840000 1.1620860000 C -0.0528710000 -2.8109730000 2.7125100000 Sn -3.0508320000 -0.3583740000 -0.3942850000 H -0.4667350000 -3.8186650000 2.6591090000 C -4.2894820000 0.1124370000 1.2774210000 H -0.3189400000 -2.3531890000 3.6737460000 H -3.8521190000 -0.2935760000 2.1964360000 H 1.0384380000 -2.8525660000 2.6169550000 158 H 0.4383900000 1.6889100000 2.2683330000 H 3.8524080000 3.2076530000 -0.1781550000 H 1.1286490000 -2.5237950000 0.0829860000 H 0.1723180000 1.2729320000 2.5152970000 Sn -2.5732820000 -1.4790280000 -0.3449920000 Sn -2.2057110000 -1.6443100000 -0.4841170000 C -1.4859060000 -2.9949360000 -1.3699620000 C -0.9965270000 -2.8431570000 -1.7593580000 H -1.1041780000 -3.7168910000 -0.6403080000 H -0.1066570000 -2.2816180000 -2.0653900000 H 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2.2100400000 4.6754740000 0.9059780000 C 2.9967150000 -1.5218350000 -0.4348440000 C 4.4659760000 -1.8463570000 -0.8872510000 C 3.4992890000 -2.6172720000 -1.1850710000 O -0.1092050000 -2.4714620000 1.2835660000 C 4.7385540000 -2.5462260000 -1.8036700000 H -0.0116210000 -0.8267500000 2.5514630000 H 2.8923670000 -3.5150560000 -1.2670150000 C 0.4000760000 -3.3209970000 2.3403750000 C 5.5109180000 -1.3649290000 -1.6845730000 H -0.1272400000 -3.1183190000 3.2813950000 H 5.1168130000 -3.3864050000 -2.3763330000 H 0.2132400000 -4.3497160000 2.0300030000 H 6.4812960000 -1.3041380000 -2.1662900000 H 1.4763010000 -3.1678190000 2.4862230000 C 5.0315820000 -0.2836180000 -0.9559030000 C 5.6211410000 -1.3732160000 -1.4897290000 H 5.6447930000 0.6072260000 -0.8847850000 H 6.3115420000 -2.0589270000 -1.9695210000 C 5.0192570000 0.9001540000 -0.8643790000 H 5.2596120000 1.9572950000 -0.8606670000 (11b) 9panth_TS_cis C 5.8996930000 0.0164400000 -1.4743370000 E = -1123.046038 H 6.8064290000 0.3896660000 -1.9388730000 No. of Negative Frequencies = 1 H 2.0953250000 -2.5079160000 0.2306340000 freq = -462.7240 H 4.2381440000 -2.9088430000 -0.8921060000

(11b-t) 9panth_TS_trans E = -1123.039181 No. of Negative Frequencies = 1 freq = -413.0162

C 1.4909940000 -0.6159450000 1.0066810000 C 1.7589180000 0.7977970000 1.0789390000 C 0.7920200000 1.6665590000 1.7131330000 C 3.0154430000 2.7613710000 0.3459850000 C 2.0794770000 3.5991350000 0.9578880000 C 0.9937410000 3.0669260000 1.6704640000 C 1.5924140000 -0.7414770000 0.8541020000 C 0.1224410000 -1.0562810000 1.4811570000 C 1.8440160000 0.6787170000 0.9054870000 C -0.9477910000 -0.3218830000 0.6602020000 C 0.8887730000 1.5414350000 1.5581500000 C -0.9569720000 1.0002270000 0.5836190000 C 3.0730020000 2.6446520000 0.1350420000 C -1.7454800000 2.0960440000 0.0790090000 C 2.1328260000 3.4782090000 0.7433990000 C -3.0680550000 2.2971780000 0.5434900000 C 1.0646570000 2.9403190000 1.4819820000 C -3.8267660000 3.3764570000 0.0780640000 C 0.2366820000 -1.2534010000 1.3028450000 C -3.2773010000 4.2788810000 -0.8491260000 C -0.8745330000 -0.5201610000 0.5382680000 C -1.9584930000 4.0977050000 -1.3012610000 C -0.8959090000 0.8062900000 0.4842550000 C -1.1920670000 3.0235390000 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-0.5395120000 H -3.9279880000 -1.8192700000 1.6888060000 C -3.8236640000 -0.2405260000 1.3037290000 H 2.2791220000 -2.6479390000 0.1786830000 H -3.3722100000 0.6363670000 1.7831600000 C 5.0952060000 0.7934300000 -1.0589570000 H -4.5515250000 0.1184870000 0.5683600000 C 4.6147180000 -1.9655470000 -0.9788760000 H -4.3581220000 -0.8176850000 2.0691970000 C 5.9966820000 -0.0894360000 -1.6397880000 H 2.1349110000 4.6453920000 -0.8947600000 C 5.7563060000 -1.4852420000 -1.6020120000 H 0.0105190000 3.6591880000 -1.6432010000 H 4.4155790000 -3.0332410000 -0.9434730000 C 3.7950780000 -0.9241140000 0.2691320000 H 6.4640060000 -2.1700120000 -2.0572740000 C 4.8046540000 -1.7592810000 0.8304180000 H 6.8915210000 0.2903360000 -2.1217490000 C 5.2623060000 1.0016620000 0.6349340000 H 5.3082920000 1.8555700000 -1.0949080000 C 6.0019370000 -1.2284330000 1.2741560000 H 2.2486100000 4.5554480000 0.6737910000 H 4.6141930000 -2.8265100000 0.9029050000 H 0.3746830000 3.5966050000 2.0020980000 C 6.2322940000 0.1700320000 1.1714170000 H 5.4635350000 2.0646990000 0.5699910000 H 6.7649760000 -1.8718260000 1.6993500000 (11c) 9panth_P_cis H 7.1726450000 0.5864170000 1.5176310000 E = -1123.0820098 No. of Negative Frequencies = 0 (11c-t) 9panth_P_trans E = -1123.0793896 No. of Negative Frequencies = 0

C 1.5987730000 -0.6713050000 -0.7486960000 C 1.7877350000 0.7337460000 -0.8320520000 C 0.6127020000 1.5344100000 -1.3743710000 C 1.7699660000 -0.7322200000 0.2608330000 C 3.0953450000 2.7641090000 -0.4352670000 C 1.9115600000 0.6734660000 0.4096920000 C 2.0156000000 3.5660680000 -0.8913120000 C 0.6957360000 1.4566450000 0.8860940000 C 0.8246730000 3.0211090000 -1.3122050000 C 3.2275220000 2.7324420000 0.1873170000 C 0.2522630000 -1.1687920000 -1.2415520000 C 2.0704490000 3.5158440000 0.4331350000 C -0.8639720000 -0.3274140000 -0.6339710000 C 0.8522660000 2.9450720000 0.7126920000 C -0.6973320000 1.0124420000 -0.7116850000 C 0.4226300000 -1.3513070000 0.5547270000 C -1.6858990000 2.0040230000 -0.2039700000 C -0.7335470000 -0.4697200000 0.1153540000 C -2.9503350000 2.1300050000 -0.8055520000 C -0.6070950000 0.8643910000 0.3023610000 C -3.8823050000 3.0615510000 -0.3207270000 C -1.7588130000 1.7778970000 0.0444750000 C -3.5574700000 3.8757250000 0.7739300000 C -2.2938150000 1.9002450000 -1.2508240000 C -2.2929960000 3.7604610000 1.3767290000 C -3.4258750000 2.6975540000 -1.4830840000 C -1.3608410000 2.8371570000 0.8851990000 C -4.0330030000 3.3840250000 -0.4210550000 160 C -3.4974780000 3.2754120000 0.8741700000 C 1.8578110000 -1.1917720000 1.8501010000 C -2.3664350000 2.4819840000 1.1028590000 C -0.8594960000 -0.9718750000 -1.5617610000 H 0.3766580000 -2.3476730000 0.0851980000 C -1.6384430000 -0.0023830000 -0.6703620000 H -1.8139320000 1.3736570000 -2.0715680000 C -1.4099690000 1.2805120000 -0.5738360000 H -3.9671140000 3.7987060000 1.7008650000 C -1.3357590000 2.6313980000 -0.2440620000 H -1.9682080000 2.3779230000 2.1091620000 C -0.4637080000 3.0682900000 0.8066800000 H -3.8286850000 2.7834940000 -2.4873500000 C -0.3738660000 4.4195080000 1.1332310000 H -4.9104640000 3.9973100000 -0.5984890000 C -1.1338610000 5.3810890000 0.4363920000 C 4.2776320000 0.4856810000 -0.2719880000 C -1.9915350000 4.9671370000 -0.6027380000 C 2.8367040000 -1.5108060000 -0.1437610000 C 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-0.4360270000 1.8055470000 H -0.9656160000 -4.3062850000 -1.2490460000 H -4.4296620000 0.4001010000 0.3397210000 H -0.8878140000 -3.3735700000 -2.7753400000 H -5.0621210000 -1.2188770000 0.7320470000 H 0.5120390000 -3.3842930000 -1.6587810000 C -2.2375720000 -3.4745580000 0.2403590000 H -0.0233780000 -1.4455070000 0.8834750000 H -1.6434110000 -4.0100630000 -0.5095410000 Sn -3.2036840000 -0.9387770000 0.4939980000 H -1.6987430000 -3.4931070000 1.1954460000 C -4.4878960000 -2.0701170000 -0.7706220000 H -3.1854510000 -4.0094730000 0.3677030000 H -3.9565650000 -2.9597330000 -1.1237810000 C -3.0181390000 -1.3794110000 -2.4304000000 H -5.3918320000 -2.3839910000 -0.2363130000 H -3.5831970000 -0.4703870000 -2.6663480000 H -4.7921470000 -1.4769250000 -1.6402150000 H -2.0972300000 -1.3794870000 -3.0245170000 C -4.2440990000 0.7259970000 1.3254930000 H -3.6196690000 -2.2463160000 -2.7274310000 H -4.9960300000 0.4048250000 2.0556610000 H -0.0187970000 3.5720880000 0.8715140000 H -3.5389890000 1.3991030000 1.8283200000 H 2.1515840000 4.5974350000 0.3804530000 H -4.7484850000 1.2993520000 0.5388420000 C 4.1142430000 -0.9273440000 -0.4018850000 C -2.4007320000 -2.1250500000 2.0698900000 C 5.2217470000 -1.7365560000 -0.7906190000 H -3.2042510000 -2.5521770000 2.6811760000 C 6.4577050000 -1.1723420000 -1.0452640000 H -1.8060370000 -2.9405410000 1.6453700000 H 5.0743900000 -2.8092170000 -0.8838010000 H -1.7603950000 -1.5203460000 2.7230710000 C 6.6267140000 0.2333560000 -0.9191630000 H 0.4741400000 -0.2153770000 -3.7548500000 H 7.2975140000 -1.7928750000 -1.3396160000 H 1.4936510000 -1.5127460000 2.8225180000 H 7.5970890000 0.6771070000 -1.1164830000 C 3.3560050000 0.0543820000 -1.9464190000 C 5.5627330000 1.0378550000 -0.5445210000 C 4.7506460000 0.4241810000 -2.0675330000 H 5.7246240000 2.1054810000 -0.4554460000 C 5.5886970000 0.3787040000 -0.9922490000 C 4.1305090000 -0.8621410000 2.8281540000 C 5.4742670000 -0.4984870000 2.6777640000 (12a) 1pyr_SM C 5.9615580000 -0.0907170000 1.4284770000 E = -1199.262719 C 5.1105750000 -0.0413080000 0.3085030000 No. of Negative Frequencies = 0 H 2.8590060000 0.4191800000 -4.0133870000 H 5.1128150000 0.7427160000 -3.0409040000 H 6.6337060000 0.6595050000 -1.0893930000 H 7.0041150000 0.1926270000 1.3151990000 H 6.1415200000 -0.5316590000 3.5325240000 H 3.7549050000 -1.1783530000 3.7971350000

(12b) 1pyr_TS_cis E = -1199.2470305 No. of Negative Frequencies = 1 freq = -453.7635

C 0.6238490000 -0.6687180000 -1.6583340000 C 1.4797460000 -0.7292390000 -0.5300320000 C 1.0129840000 -1.1483560000 0.7782550000 C 3.7388120000 -0.4106780000 0.4538130000 C 3.2506780000 -0.8233290000 1.7290880000 161 H 4.0515090000 -3.7350510000 -1.8474420000 H 5.9129760000 -2.1042940000 -1.8396160000

(12b-t) 1pyr_TS_trans E = -1199.239994 No. of Negative Frequencies = 1 freq = -392.1847

C 0.3204720000 -1.9127490000 0.7386980000 C 1.4168430000 -1.0409960000 0.8624740000 C 1.2975850000 0.2112970000 1.6094350000 C 3.6879280000 -0.3607480000 0.1303820000 C 3.5468660000 0.8814070000 0.8308400000 C 2.3592080000 1.1182580000 1.6014600000 C -1.0081590000 -1.4209940000 1.2677690000

C -1.3784620000 -0.0976860000 0.5744950000 C 0.5799720000 -2.0366850000 0.4658550000 C -0.5486360000 0.9307900000 0.5703850000 C 1.5434470000 -1.0272530000 0.6595280000 C -0.4368950000 2.3251180000 0.2334020000 C 1.2441680000 0.1475820000 1.4751540000 C -1.3004590000 3.2771160000 0.8297530000 C 3.7093070000 -0.0025540000 0.0196830000 C -1.1682110000 4.6379510000 0.5335670000 C 3.3811280000 1.1695570000 0.7740100000 C -0.1682160000 5.0751890000 -0.3519680000 C 2.1585980000 1.1952220000 1.5287630000 C 0.7046500000 4.1396260000 -0.9349490000 C -0.8410520000 -1.8058190000 0.9384590000 C 0.5814800000 2.7777170000 -0.6392690000 C -1.3935630000 -0.4939910000 0.3550200000 H -2.0709810000 2.9323890000 1.5139360000 C -0.7007770000 0.6324690000 0.4321660000 H 1.4821820000 4.4734850000 -1.6144160000 C -0.8348670000 2.0482350000 0.2070580000 H 1.2603050000 2.0525200000 -1.0793030000 C -1.8396240000 2.7875440000 0.8797800000 H -1.8434990000 5.3568250000 0.9866850000 C -1.9622170000 4.1662140000 0.6701620000 H -0.0674700000 6.1310290000 -0.5811420000 C -1.0829120000 4.8298530000 -0.2023350000 C 2.7345610000 -2.5309550000 -0.5940170000 C -0.0687990000 4.1065960000 -0.8557680000 C 0.4312820000 -3.0889220000 -0.0225260000 C 0.0648540000 2.7300220000 -0.6457780000 C 1.6348900000 -3.4128070000 -0.6513020000 H -1.4560300000 -2.6584660000 0.6080000000 C 2.6165960000 -1.3176190000 0.1473290000 H -2.5055110000 2.2689240000 1.5650140000 H 0.5825050000 0.2710820000 2.4262770000 H 0.6178180000 4.6177930000 -1.5227940000 Sn -3.2363460000 -0.1934110000 -0.5162250000 H 0.8528870000 2.1672820000 -1.1382580000 C -3.0793220000 -1.6623940000 -2.0449490000 H -2.7394850000 4.7224650000 1.1844520000 H -2.9879310000 -2.6499560000 -1.5831000000 H -1.1808720000 5.8982250000 -0.3653120000 H -3.9581530000 -1.6481220000 -2.6998190000 C 0.8941310000 -3.1638300000 -0.3124290000 H -2.1881200000 -1.4808920000 -2.6559810000 C 2.1436710000 -3.2883460000 -0.9264520000 C -3.4863680000 1.7275600000 -1.4132410000 C 2.7848630000 -1.1011950000 -0.0342350000 H -4.2587190000 1.6827540000 -2.1911510000 O -0.9724350000 -1.6980050000 2.3889940000 H -3.7865440000 2.4767070000 -0.6719360000 C -0.5248860000 -2.8849160000 3.0900530000 H -2.5519090000 2.0704910000 -1.8729510000 H -0.7557950000 -2.7252230000 4.1435900000 C -4.8657490000 -0.5648740000 0.8034360000 H -1.0562220000 -3.7762320000 2.7261850000 H -4.8131430000 0.0930920000 1.6782810000 H 0.5542750000 -3.0346510000 2.9622140000 H -5.8249490000 -0.3918110000 0.3021220000 H 0.4934760000 0.0494550000 2.2533660000 H -4.8271470000 -1.6037800000 1.1466270000 Sn -3.3215360000 -0.4609880000 -0.5914230000 H 2.3017480000 2.0248660000 2.1973790000 C -3.6920840000 -2.4525870000 -1.2601930000 O -2.0913370000 -2.3414600000 0.9918670000 H -3.8860290000 -3.1200890000 -0.4127430000 H -0.9595030000 -1.2529010000 2.3569190000 H -4.5662820000 -2.4803500000 -1.9206770000 C -2.2395600000 -3.4080750000 1.9603510000 H -2.8312570000 -2.8394070000 -1.8181630000 H -2.5278200000 -2.9998600000 2.9374590000 C -3.2372710000 0.9138520000 -2.2089900000 H -3.0302110000 -4.0602610000 1.5875170000 H -4.1574820000 0.8828760000 -2.8032090000 H -1.3085200000 -3.9788780000 2.0648980000 H -3.1022580000 1.9329800000 -1.8289140000 C 4.8813060000 -0.6391460000 -0.5945230000 H -2.3908060000 0.6815100000 -2.8643190000 C 5.9192680000 0.3175630000 -0.6140570000 C -4.8030190000 0.1291280000 0.8223920000 C 5.7774770000 1.5323980000 0.0688760000 H -5.7918820000 -0.2468910000 0.5367080000 C 4.6059560000 1.8148470000 0.7839040000 H -4.5549470000 -0.2611560000 1.8153390000 H 6.8288100000 0.1028760000 -1.1677900000 H -4.8551540000 1.2222170000 0.8818550000 H 6.5813380000 2.2608700000 0.0444000000 H 0.1431620000 -3.9382710000 -0.4506730000 H 4.5015540000 2.7581720000 1.3124190000 H 1.9626090000 2.0517980000 2.1679140000 H 1.7200920000 -4.3292220000 -1.2284480000 C 3.0937410000 -2.2521940000 -0.8203670000 H -0.4418620000 -3.7212200000 -0.1469450000 C 4.3635730000 -2.3069330000 -1.5109860000 C 3.9661230000 -2.7992280000 -1.3020430000 C 5.2469660000 -1.2670170000 -1.4467950000 C 4.9927930000 -1.8977590000 -1.3001340000 C 4.2972840000 2.2434580000 0.7989450000 162 C 5.5089200000 2.1673530000 0.0996210000 H -2.3673640000 -3.3488830000 2.5236630000 C 5.8339100000 1.0209600000 -0.6376570000 H -2.6762240000 -4.4172650000 1.1232050000 C 4.9433430000 -0.0723020000 -0.6879390000 H -1.0173870000 -4.2520000000 1.7709680000 H 2.3798090000 -4.1679440000 -1.5185370000 C 5.0809920000 -0.1853920000 -0.3959980000 H 4.5949630000 -3.1952860000 -2.0921980000 C 6.0059010000 0.8945100000 -0.3640410000 H 6.1961120000 -1.3134230000 -1.9736240000 C 5.6254870000 2.1336670000 0.1588750000 H 6.7740320000 0.9659050000 -1.1791330000 C 4.3303150000 2.3301240000 0.6590600000 H 6.2012670000 3.0022280000 0.1304050000 H 7.0073560000 0.7459720000 -0.7572410000 H 4.0510210000 3.1326250000 1.3723690000 H 6.3361360000 2.9534900000 0.1756630000 H 4.0384240000 3.2983570000 1.0559750000 H 2.5166340000 -4.3075620000 -1.0753120000 (12c) 1pyr_P_cis H 0.1911880000 -3.9598120000 -0.2382350000 E = -1199.287139 C 4.5386310000 -2.4922840000 -1.0191250000 No. of Negative Frequencies = 0 C 5.4420760000 -1.4672820000 -0.9579020000 H 4.8142700000 -3.4477760000 -1.4568620000 H 6.4497140000 -1.5937940000 -1.3438090000

(12c-t) 1pyr_P_trans E = -1199.284796 No. of Negative Frequencies = 0

C 0.5946280000 -1.9664100000 0.4969150000 C 1.5194730000 -0.9329020000 0.5958920000 C 1.0481870000 0.3690770000 1.2229370000 C 3.7764800000 -0.0038570000 0.1186350000 C 3.3774910000 1.2756980000 0.6561590000 C 2.0707190000 1.4656380000 1.1542670000 C 0.8754090000 -1.9974750000 0.0833050000 C -0.7926030000 -1.6584610000 1.0293690000 C 1.6456650000 -0.8580510000 0.2911310000 C -1.2561240000 -0.2876800000 0.5426230000 C 0.9814560000 0.3472020000 0.9308660000 C -0.3596450000 0.7183300000 0.6553230000 C 3.8034450000 0.3613810000 0.0362180000 C -0.6577660000 2.1353280000 0.3068060000 C 3.1901700000 1.5756320000 0.5199180000 C -1.6216080000 2.8541830000 1.0358710000 C 1.8284880000 1.5865320000 0.8895670000 C -1.9157100000 4.1879470000 0.7128330000 C -0.5871950000 -1.9566090000 0.4742540000 C -1.2476340000 4.8169910000 -0.3475820000 C -1.2186950000 -0.6021550000 0.1851460000 C -0.2772900000 4.1083530000 -1.0771310000 C -0.4696330000 0.5001100000 0.4197760000 C 0.0217780000 2.7800230000 -0.7463390000 C -1.0414870000 1.8713190000 0.2741010000 H -2.1390950000 2.3608460000 1.8545540000 C -2.0806690000 2.2957690000 1.1228880000 H 0.2413870000 4.5892170000 -1.9003280000 C -2.6758780000 3.5558100000 0.9487050000 H 0.7715500000 2.2314600000 -1.3105420000 C -2.2343190000 4.4047590000 -0.0767650000 H -2.6662630000 4.7289360000 1.2802510000 C -1.1860370000 3.9938260000 -0.9183770000 H -1.4783300000 5.8460410000 -0.6039320000 C -0.5895550000 2.7387130000 -0.7395230000 C 3.1973730000 -2.3329000000 -0.5102100000 H -1.1173350000 -2.7687270000 -0.0481670000 C 0.9440010000 -3.1872650000 -0.1212470000 H -2.4133150000 1.6367530000 1.9209550000 C 2.2350070000 -3.3704290000 -0.6033040000 H -0.8414160000 4.6466330000 -1.7137650000 C 2.8287600000 -1.0904500000 0.0797220000 H 0.2137920000 2.4160550000 -1.3962210000 H 0.8594550000 0.1630600000 2.2979780000 H -3.4782190000 3.8700550000 1.6086480000 Sn -3.1769740000 -0.3282890000 -0.4119980000 H -2.6968470000 5.3763040000 -0.2179490000 C -3.0565220000 -1.5801850000 -2.1264500000 C 1.4548660000 -3.1547780000 -0.4882200000 H -2.6874900000 -2.5636050000 -1.8223990000 C 2.7995080000 -3.1690200000 -0.8336750000 H -4.0404060000 -1.6905690000 -2.5975450000 C 3.0116420000 -0.8385400000 -0.0936090000 H -2.3665530000 -1.1576020000 -2.8653830000 O -0.7731530000 -2.1623370000 1.9180780000 C -3.7660980000 1.6079260000 -1.0924170000 C -0.3254870000 -3.4593670000 2.3824880000 H -4.5607750000 1.4945660000 -1.8409440000 H -0.6280180000 -3.5327310000 3.4277290000 H -4.1456590000 2.2270570000 -0.2726630000 H -0.8005300000 -4.2658920000 1.8042760000 H -2.9270760000 2.1417980000 -1.5545650000 H 0.7642850000 -3.5576320000 2.3044980000 C -4.6343760000 -1.0278450000 0.9783500000 H 0.8384320000 0.0877530000 2.0001920000 H -4.4992850000 -0.5536480000 1.9577000000 Sn -3.2555370000 -0.5578890000 -0.4574200000 H -5.6490830000 -0.8059250000 0.6284880000 C -3.6219230000 -2.5101730000 -1.2413950000 H -4.5332480000 -2.1117570000 1.0995620000 H -3.5733130000 -3.2631520000 -0.4452870000 H 1.7935610000 2.4399890000 1.5483190000 H -4.6192480000 -2.5612400000 -1.6934920000 O -1.7760630000 -2.6451310000 0.6343760000 H -2.8874120000 -2.7729500000 -2.0119830000 H -0.7465620000 -1.6289880000 2.1364840000 C -3.5434220000 0.9211670000 -1.9595960000 C -1.9622020000 -3.7288000000 1.5767520000 163 H -4.5367010000 0.8261180000 -2.4135940000 H 0.8460730000 -3.5681780000 -0.6325780000 H -3.4503320000 1.9248000000 -1.5270570000 H -0.3580450000 -1.3580860000 1.4427560000 H -2.7896730000 0.8196500000 -2.7484200000 Sn -3.2697220000 -0.9065140000 0.0232880000 C -4.5753060000 -0.2314620000 1.1857790000 C -4.1052890000 -2.1965300000 -1.4485410000 H -5.5220550000 -0.7622760000 1.0343290000 H -3.5065550000 -3.1110530000 -1.5076620000 H -4.1159370000 -0.5984100000 2.1106340000 H -5.1392500000 -2.4626200000 -1.2009210000 H -4.7920620000 0.8366780000 1.3000950000 H -4.1024170000 -1.7122660000 -2.4315470000 H 0.8362660000 -4.0341540000 -0.6513080000 C -4.4886900000 0.8265570000 0.2627940000 H 1.3910180000 2.5117620000 1.2552220000 H -5.4794860000 0.5674830000 0.6543020000 C 3.5982140000 -2.0126120000 -0.6473550000 H -4.0192560000 1.5362530000 0.9546670000 C 4.9930050000 -1.9917630000 -1.0180480000 H -4.6206790000 1.3375240000 -0.6983470000 C 5.7450530000 -0.8602350000 -0.8658060000 C -3.0433320000 -1.8810410000 1.9027150000 C 3.9904680000 2.7473840000 0.6032100000 H -4.0138700000 -2.2194730000 2.2834970000 C 5.3431020000 2.7255000000 0.2352430000 H -2.3849740000 -2.7484550000 1.7888010000 C 5.9329120000 1.5488880000 -0.2347460000 H -2.6063810000 -1.1981010000 2.6409450000 C 5.1650720000 0.3571640000 -0.3469420000 H 1.5498410000 -0.6597120000 -2.9194380000 H 3.2511880000 -4.0597890000 -1.2608130000 C 5.1393450000 0.1286940000 -0.0890250000 H 5.4313340000 -2.8989200000 -1.4246580000 C 4.1712460000 -0.0104390000 -2.7402610000 H 6.7945460000 -0.8505230000 -1.1472630000 C 5.9911350000 0.3901730000 -1.1795570000 H 6.9790840000 1.5344200000 -0.5265320000 C 5.5100130000 0.3210900000 -2.4932850000 H 5.9344400000 3.6320840000 0.3128080000 H 3.8003060000 -0.0603010000 -3.7600190000 H 3.5369060000 3.6669610000 0.9622660000 H 6.1771860000 0.5270150000 -3.3235270000 H 7.0295020000 0.6478180000 -0.9907390000 H 2.8811810000 -0.6214090000 4.1873520000 (13a) 4pyr_SM H 0.5033420000 -1.2231110000 3.7593370000 E = -1199.263566 C 5.6077520000 0.1926530000 1.2789920000 No. of Negative Frequencies = 0 C 4.7650780000 -0.0645260000 2.3208250000 H 5.1204120000 -0.0158040000 3.3464210000 H 6.6480870000 0.4507430000 1.4562160000

(13b) 4pyr_TS_cis E = -1199.247895 No. of Negative Frequencies = 1 freq = -465.1400

C 1.0440450000 -0.8729030000 -0.8634240000 C 1.5154750000 -0.8176100000 0.5167900000 C 0.6752950000 -1.0837680000 1.6174290000 C 3.3762970000 -0.4095860000 2.0979550000 C 2.5044740000 -0.6762230000 3.1697990000 C 1.1677000000 -1.0119770000 2.9275290000 C -0.4110030000 -1.1508330000 -1.1857260000 C -1.3853130000 -0.0957610000 -0.6656780000 C -1.1533460000 1.1904550000 -0.6075500000 C -1.2861850000 2.5534280000 -0.3229710000 C 1.0516480000 -1.0116240000 1.0708950000 C -0.8554300000 3.0662580000 0.9419460000 C 1.5877060000 0.3203350000 1.1853680000 C -0.9780040000 4.4241520000 1.2321650000 C 0.8279490000 1.3595570000 1.8132080000 C -1.5198710000 5.3154530000 0.2843650000 C 3.2935600000 1.9783900000 0.5144680000 C -1.9389840000 4.8259070000 -0.9685970000 C 2.5206660000 2.9940000000 1.1368960000 C -1.8249550000 3.4710600000 -1.2776440000 C 1.3313350000 2.6937410000 1.7858070000 H -0.5112580000 -1.2184470000 -2.2812710000 C -0.3851040000 -1.1800030000 1.5112690000 H -0.4283800000 2.3775250000 1.6650920000 C -1.2727800000 -0.2427320000 0.6750210000 H -2.3562370000 5.5096550000 -1.7012330000 C -1.0399630000 1.0570830000 0.6154600000 H -2.1488480000 3.0944820000 -2.2427560000 C -1.5493130000 2.3016980000 0.1082950000 H -0.6491260000 4.7968660000 2.1971040000 C -2.7933390000 2.8086070000 0.5603670000 H -1.6104240000 6.3712520000 0.5162780000 C -3.2737920000 4.0333730000 0.0844580000 C 3.7748580000 -0.2094930000 -0.3338080000 C -2.5218470000 4.7784490000 -0.8403850000 C 1.9070500000 -0.6191820000 -1.8920320000 C -1.2780100000 4.2920850000 -1.2805690000 C 3.2934120000 -0.2773570000 -1.6736450000 C -0.7878710000 3.0709350000 -0.8053710000 C 2.8843190000 -0.4812520000 0.7585820000 H -3.3719710000 2.2267430000 1.2723440000 O -0.9036560000 -2.4012450000 -0.6129050000 H -0.6924220000 4.8665390000 -1.9910670000 C -0.1774680000 -3.5828230000 -1.0248540000 H 0.1760680000 2.6938280000 -1.1356040000 H -0.7177960000 -4.4369190000 -0.6148590000 H -4.2336920000 4.4058380000 0.4279120000 H -0.1453380000 -3.6544930000 -2.1207260000 H -2.8981960000 5.7265940000 -1.2104270000

164 C 3.5511240000 -0.3998760000 -0.1330540000 C -1.9375230000 4.0491710000 -1.2794410000 C 1.7391780000 -1.9920630000 0.3997520000 C -1.2272930000 2.8969940000 -0.9251430000 C 3.0297390000 -1.7290050000 -0.1845010000 H -0.3687150000 -2.4542520000 1.0268070000 C 2.8089360000 0.6340340000 0.5267750000 H -3.4211500000 1.5966420000 1.3572330000 H 0.0987250000 1.1128380000 2.5802360000 H -1.5197420000 4.7353990000 -2.0091090000 Sn -2.7206090000 -1.2854180000 -0.5363140000 H -0.2572380000 2.6842330000 -1.3651070000 C -1.6944860000 -2.6186940000 -1.8366930000 H -4.6790110000 3.6533740000 0.7212300000 H -1.4262740000 -3.5220250000 -1.2800750000 H -3.7310560000 5.2220090000 -0.9691270000 H -2.3095330000 -2.8932980000 -2.7011720000 C 3.7241370000 -0.2792520000 -0.2509190000 H -0.7709800000 -2.1530880000 -2.1988990000 C 2.0467040000 -1.9977770000 0.3130260000 C -3.7001920000 0.2289310000 -1.6765060000 C 3.3361610000 -1.6538740000 -0.2340880000 H -4.2602030000 -0.2200080000 -2.5060130000 C 2.8655900000 0.7136380000 0.3272820000 H -4.3996640000 0.8004320000 -1.0560410000 O -0.5116310000 -1.1642880000 2.6546310000 H -2.9715720000 0.9356310000 -2.0912990000 C 0.3122720000 -1.9488930000 3.5527760000 C -4.1499570000 -2.2926080000 0.6775150000 H -0.0938300000 -1.7969490000 4.5531680000 H -4.5795480000 -1.6117650000 1.4209810000 H 0.2655050000 -3.0162990000 3.2930580000 H -4.9673420000 -2.6950660000 0.0682600000 H 1.3578300000 -1.6191820000 3.5190400000 H -3.6584120000 -3.1183270000 1.2021070000 H 0.0958980000 1.0043950000 2.3184620000 H 0.7714610000 3.4782360000 2.2844330000 Sn -2.8109620000 -1.4440490000 -0.6052920000 H 2.8882180000 4.0165540000 1.1216780000 C -2.0967930000 -3.3494180000 -1.2479630000 C 3.7710680000 -2.7324960000 -0.8439780000 H -2.0420180000 -4.0502230000 -0.4069780000 O -0.8831720000 -2.5205390000 1.2888670000 H -2.7640450000 -3.7786540000 -2.0040170000 H -0.4981660000 -0.9359440000 2.5805480000 H -1.0971500000 -3.2545790000 -1.6878460000 C -0.5668480000 -3.4645380000 2.3411370000 C -3.3361210000 -0.1996800000 -2.2445720000 H -1.0634840000 -3.1752820000 3.2761380000 H -4.0676930000 -0.6915250000 -2.8956250000 H -0.9415310000 -4.4344300000 2.0121600000 H -3.7658720000 0.7419070000 -1.8843560000 H 0.5157870000 -3.5228330000 2.5067770000 H -2.4477400000 0.0418720000 -2.8385610000 C 5.0027090000 -2.4332650000 -1.4393380000 C -4.4453160000 -1.6965340000 0.7382980000 H 5.5624760000 -3.2163950000 -1.9400480000 H -4.9506370000 -0.7393270000 0.9086720000 C 4.7972440000 -0.0967450000 -0.7610690000 H -5.1782500000 -2.4077540000 0.3409910000 C 5.5137670000 -1.1286820000 -1.4021810000 H -4.0832660000 -2.0691920000 1.7027830000 H 6.4654260000 -0.9010160000 -1.8738620000 H 1.7110680000 -3.0307380000 0.2364290000 H 1.2857440000 -2.9693760000 0.2574580000 C 4.9627780000 0.1037250000 -0.8493160000 H 3.3730280000 -3.7421160000 -0.8895870000 C 4.2002560000 -2.6212140000 -0.7873360000 C 5.2787040000 1.2651480000 -0.7285790000 C 5.8022140000 -0.8919830000 -1.3895670000 C 4.5510170000 2.2583290000 -0.1256650000 C 5.4238420000 -2.2409350000 -1.3530210000 H 6.2294510000 1.4866900000 -1.2052600000 H 3.9056310000 -3.6669250000 -0.7742830000 H 4.9153720000 3.2820730000 -0.1197370000 H 6.0818090000 -2.9952310000 -1.7717400000 H 6.7486510000 -0.6019050000 -1.8370830000 H 2.6428640000 4.1103400000 0.7794140000 (13b-t) 4pyr_TS_trans H 0.5664350000 3.4321140000 1.9508810000 E = -1199.240259 C 5.3154360000 1.5051170000 -0.8816380000 No. of Negative Frequencies = 1 C 4.4819790000 2.4550840000 -0.3528600000 freq = -408.9961 H 4.7531520000 3.5069580000 -0.3877610000 H 6.2582090000 1.7888100000 -1.3409320000

(13c) 4pyr_P_cis E = -1199.2905504 No. of Negative Frequencies = 0

C 1.2303470000 -1.0513370000 0.8796180000 C 1.6534340000 0.3258890000 0.9638260000 C 0.8163480000 1.3133260000 1.5673060000 C 3.2342910000 2.0932300000 0.2686440000 C 2.3646470000 3.0609160000 0.8325160000 C 1.1973870000 2.6818640000 1.4852220000 C -0.2005180000 -1.3869910000 1.2457410000 C 1.2636440000 -1.0015580000 0.7212600000 C -1.1817730000 -0.5177830000 0.4432940000 C 1.6181910000 0.3586780000 0.8111980000 C -1.0574900000 0.8005640000 0.4017930000 C 0.5661440000 1.3247990000 1.3234940000 C -1.7711740000 1.9847100000 0.0114540000 C 3.2457060000 2.1797220000 0.4148610000 C -3.0207480000 2.2813130000 0.6140660000 C 2.2386930000 3.1409760000 0.8384390000 C -3.7202180000 3.4400240000 0.2594210000 C 0.9942310000 2.7684850000 1.2256520000 C -3.1859410000 4.3253490000 -0.6931020000 C -0.1481440000 -1.3271460000 1.1719280000 C -1.1409240000 -0.3304340000 0.5804770000 165 C -0.8008000000 0.9756740000 0.6684700000 C 3.2131840000 2.2095780000 0.2995080000 C -1.6741980000 2.0932340000 0.2114200000 C 2.1361180000 3.1115920000 0.6779690000 C -2.8692420000 2.3827890000 0.8933330000 C 0.8985630000 2.6661160000 1.0051350000 C -3.6961100000 3.4355670000 0.4721710000 C -0.0192980000 -1.5362550000 0.7710830000 C -3.3354580000 4.2091000000 -0.6407720000 C -1.0753680000 -0.5388960000 0.3148450000 C -2.1397560000 3.9299630000 -1.3246030000 C -0.8045660000 0.7756980000 0.4952880000 C -1.3103840000 2.8850980000 -0.8957820000 C -1.8325950000 1.8206920000 0.2160430000 H -3.1478010000 1.7769330000 1.7515750000 C -3.0300870000 1.8295890000 0.9566160000 H -1.8574210000 4.5233010000 -2.1884520000 C -4.0418590000 2.7591900000 0.6705300000 H -0.3845600000 2.6692790000 -1.4219430000 C -3.8643370000 3.6930370000 -0.3610920000 H -4.6181770000 3.6454770000 1.0047170000 C -2.6655090000 3.7001170000 -1.0954140000 H -3.9765050000 5.0192310000 -0.9728990000 C -1.6541490000 2.7748900000 -0.8048970000 C 3.8317590000 -0.1715440000 -0.1081390000 H -0.1881310000 -2.5349720000 0.3385930000 C 2.1494100000 -1.9411280000 0.2084030000 H -3.1573420000 1.1087890000 1.7605110000 C 3.4590570000 -1.5495960000 -0.2014080000 H -2.5244490000 4.4201180000 -1.8950190000 C 2.8931550000 0.7893070000 0.3830890000 H -0.7322270000 2.7729100000 -1.3798000000 H 0.4132030000 1.1118400000 2.4022180000 H -4.9601700000 2.7536620000 1.2490630000 Sn -2.7915830000 -1.2647550000 -0.4218840000 H -4.6467580000 4.4096850000 -0.5889280000 C -2.0560300000 -2.4043060000 -2.0595450000 C 3.9507030000 -0.0955080000 -0.2323290000 H -1.3318590000 -3.1348840000 -1.6879480000 C 2.3518840000 -1.9507720000 -0.0451330000 H -2.8742030000 -2.9288860000 -2.5670480000 C 3.6627720000 -1.4902380000 -0.3655320000 H -1.5585960000 -1.7559760000 -2.7894680000 C 2.9352910000 0.8033010000 0.2255560000 C -4.1492600000 0.1861650000 -1.2030690000 O -0.1937510000 -1.6413770000 2.2265470000 H -4.8086230000 -0.2964580000 -1.9358970000 C 0.6679100000 -2.6269460000 2.8468830000 H -4.7690560000 0.6195910000 -0.4107740000 H 0.3555310000 -2.6943440000 3.8896460000 H -3.6193920000 1.0070000000 -1.7009470000 H 0.5500080000 -3.6077030000 2.3630280000 C -3.8592210000 -2.4790240000 0.9688160000 H 1.7214640000 -2.3267670000 2.7937790000 H -4.0888220000 -1.9185540000 1.8827480000 H 0.4382970000 0.9641130000 2.1695380000 H -4.8048400000 -2.8259900000 0.5361930000 Sn -2.8958280000 -1.2834630000 -0.5199550000 H -3.2554370000 -3.3525170000 1.2369570000 C -2.4118330000 -3.2456970000 -1.2099270000 H 0.2656710000 3.5180040000 1.5228190000 H -2.2128190000 -3.9185120000 -0.3670890000 H 2.5081230000 4.1943930000 0.8230500000 H -3.2436670000 -3.6657910000 -1.7872600000 C 4.4051300000 -2.4852300000 -0.7059210000 H -1.5259340000 -3.2285660000 -1.8558120000 O -0.5610460000 -2.6631980000 0.8011340000 C -3.5226970000 -0.0509720000 -2.1362770000 H -0.1900280000 -1.2373000000 2.2757970000 H -4.3003310000 -0.5465890000 -2.7289160000 C -0.3108160000 -3.6786540000 1.8032820000 H -3.9215040000 0.8981860000 -1.7575930000 H -0.9092410000 -3.4854740000 2.7033610000 H -2.6752310000 0.1752770000 -2.7930140000 H -0.6094960000 -4.6306810000 1.3626150000 C -4.4264300000 -1.4422100000 0.9570790000 H 0.7514720000 -3.7144680000 2.0756120000 H -5.0803270000 -2.2964510000 0.7475470000 C 5.6798870000 -2.0671980000 -1.0960520000 H -3.9778560000 -1.5831020000 1.9470260000 H 6.3911740000 -2.7932980000 -1.4760230000 H -5.0393270000 -0.5339250000 0.9759300000 C 5.1364500000 0.2510400000 -0.5222060000 H 2.1193010000 -3.0074630000 -0.1637610000 C 6.0501710000 -0.7159570000 -1.0073100000 C 5.2523850000 0.4020250000 -0.5650450000 H 7.0414350000 -0.3990130000 -1.3181240000 C 4.6868370000 -2.3678580000 -0.8181050000 H 1.8382180000 -2.9752000000 0.0922860000 C 6.2439250000 -0.5071640000 -1.0074200000 H 4.1228030000 -3.5312530000 -0.7824560000 C 5.9564530000 -1.8757840000 -1.1295450000 C 5.4680270000 1.6421350000 -0.4412530000 H 4.4682740000 -3.4269690000 -0.9195520000 C 4.5376310000 2.5738960000 0.0063100000 H 6.7284400000 -2.5568630000 -1.4723820000 H 6.4588220000 1.9608310000 -0.7516470000 H 7.2326070000 -0.1321020000 -1.2557080000 H 4.7989800000 3.6282940000 0.0395750000 H 2.3485390000 4.1778980000 0.6822010000 H 0.1193400000 3.3708130000 1.2818060000 C 5.5039090000 1.8066840000 -0.4440640000 (13c-t) 4pyr_P_trans C 4.5018370000 2.6785590000 -0.0331200000 E = -1199.288203 H 4.7034380000 3.7444090000 0.0315260000 No. of Negative Frequencies = 0 H 6.4919180000 2.1830660000 -0.6929050000

(14a) nap_SM_F E = -954.2505570 No. of Negative Frequencies = 0

C 1.3780330000 -1.0716160000 0.4165620000 C 1.6598140000 0.3006680000 0.5705400000 C 0.5574910000 1.1990740000 1.0930880000

166

C -1.9905400000 -0.7629960000 -1.2594450000 C -1.4512090000 -1.9697150000 -0.5908360000 C -2.6017880000 -0.6127580000 0.0324670000 C -2.4557070000 -0.9645890000 -0.5433860000 C -1.9308790000 -0.9427340000 1.2506380000 C -2.3032750000 0.2692130000 -1.2902910000 C -4.5619170000 0.0494010000 1.3794580000 C -4.4866950000 -0.0486240000 0.5078420000 C -3.8845980000 -0.2637090000 2.5415270000 C -4.3146190000 1.1424190000 -0.1871440000 C -2.5540940000 -0.7696060000 2.4720090000 C -3.2551250000 1.2952530000 -1.1114640000 C -0.5538690000 -1.1918520000 -1.4049400000 C -0.1759470000 -1.5949780000 -1.2974670000 C 0.4759530000 -0.2833860000 -0.7474750000 C 0.4400710000 -0.3377430000 -0.6754650000 C 0.3870330000 1.0238800000 -0.7096850000 C -0.2727520000 0.7727180000 -0.5640890000 C 0.6981720000 2.3484530000 -0.3711290000 C -0.1741380000 2.1601410000 -0.1947020000 C 1.4826980000 3.1783320000 -1.2284810000 C 0.6473180000 3.0441470000 -0.9367770000 C 1.7722920000 4.4934660000 -0.8650650000 C 0.7136150000 4.4004800000 -0.5996960000 C 1.2896240000 5.0266840000 0.3461570000 C -0.0422170000 4.9000910000 0.4748000000 C 0.5043720000 4.2226070000 1.1958090000 C -0.8744800000 4.0332060000 1.2046650000 C 0.2045410000 2.9053790000 0.8495940000 C -0.9524210000 2.6773440000 0.8684870000 H 1.8534900000 2.7684940000 -2.1628390000 H 1.2291550000 2.6519220000 -1.7664540000 H 0.1265820000 4.6302720000 2.1280920000 H -1.4645300000 4.4172360000 2.0305590000 H -0.4099100000 2.2850040000 1.4956410000 H -1.6036060000 2.0051370000 1.4202920000 H 2.3769990000 5.1105450000 -1.5220770000 H 1.3536690000 5.0665190000 -1.1695660000 H 1.5186280000 6.0508930000 0.6206350000 H 0.0116110000 5.9518850000 0.7361080000 C -4.6418700000 0.2032380000 -1.0990020000 C -3.6901020000 -2.3514140000 1.0625690000 C -2.7019590000 -0.4476680000 -2.4021840000 C -1.5851440000 -3.1455010000 0.1324990000 C -4.0378060000 0.0402300000 -2.3278210000 C -2.7348310000 -3.3476630000 0.9415730000 C -3.9416470000 -0.1183620000 0.1041620000 C -3.5592140000 -1.1270750000 0.3428380000 H -5.5798950000 0.4275480000 1.4173020000 H -5.3251890000 -0.1769830000 1.1865060000 H -5.6590340000 0.5785340000 -1.0273920000 H -4.5430080000 -2.4826530000 1.7228120000 H -0.9269240000 -1.3485180000 1.2100130000 H -1.7293100000 0.2652430000 -2.2146120000 Sn 2.1846190000 -1.2527600000 0.1667480000 Sn 2.3877880000 -0.5876800000 0.2247930000 C 3.5130680000 0.3481080000 0.6071750000 C 2.1833240000 -2.0571330000 1.7487540000 H 3.0478980000 1.0526350000 1.3065570000 H 2.0558480000 -3.0441180000 1.2927800000 H 4.4424690000 -0.0209230000 1.0558750000 H 3.0643260000 -2.0778910000 2.4002220000 H 3.7651720000 0.9029070000 -0.3038310000 H 1.3017210000 -1.8447000000 2.3636480000 C 3.0119470000 -2.6214850000 -1.2339770000 C 2.9167870000 1.2936340000 1.0665760000 H 3.8902000000 -3.1267190000 -0.8168570000 H 3.8131020000 1.1904570000 1.6899910000 H 2.2630180000 -3.3784440000 -1.4890360000 H 3.1202800000 2.0348260000 0.2862630000 H 3.3162360000 -2.1050270000 -2.1506490000 H 2.1035680000 1.6830930000 1.6897470000 C 1.5795990000 -2.2407850000 1.9517730000 C 3.7873170000 -1.1879970000 -1.2588590000 H 0.8424300000 -3.0163360000 1.7185580000 H 3.8615900000 -0.4395160000 -2.0550780000 H 2.4398550000 -2.7128990000 2.4400250000 H 4.7834090000 -1.3254960000 -0.8231690000 H 1.1348670000 -1.5303020000 2.6584040000 H 3.4633100000 -2.1362990000 -1.6993860000 H -2.0319480000 -1.0301110000 3.3871470000 H -3.1781230000 2.2049540000 -1.6978950000 H -4.3608320000 -0.1338480000 3.5078030000 H -5.0225460000 1.9541030000 -0.0530160000 H -0.3108500000 -1.3363490000 -2.4622840000 H -0.3084860000 -1.4749340000 -2.3784630000 H -2.2346640000 -0.5665010000 -3.3760540000 H -0.7988880000 -3.8907810000 0.0966920000 H -4.5706290000 0.2832150000 -3.2405670000 H -2.8408040000 -4.2754220000 1.4937700000 F -0.3637910000 -2.5169660000 -0.8023640000 F 0.7889070000 -2.6677640000 -1.1548860000

(14b) nap_TS_cis_F (14b-t) nap_TS_trans_F E = -954.2354891 E = -954.2291855 No. of Negative Frequencies = 1 No. of Negative Frequencies = 1 freq = -464.9359 freq = -415.5395

167

C -2.2939550000 -1.3929210000 -0.2688380000 C 3.4194940000 -2.7727330000 -1.1188480000 C -2.7457960000 -0.0689160000 -0.3074440000 C 2.2585860000 -2.8339590000 -0.3011860000 C -1.8180500000 1.0226120000 -0.8294450000 C 4.1366950000 -1.5926700000 -1.2131880000 C -4.5025270000 1.6089190000 0.1868790000 C 1.8707890000 -1.7348590000 0.4507050000 C -3.5896550000 2.6576950000 -0.0656780000 C 2.6462140000 -0.5399330000 0.4329080000 C -2.2973800000 2.4127470000 -0.4841640000 C 3.7532170000 -0.4431500000 -0.4581950000 C -0.8742630000 -1.6731580000 -0.7010840000 C 4.4334330000 0.8092090000 -0.5961620000 C 0.0943540000 -0.5560940000 -0.3855330000 H 5.2782470000 0.8759120000 -1.2760030000 C -0.3556200000 0.7180850000 -0.4323800000 C 4.0168910000 1.9194420000 0.1268840000 C 0.5394040000 1.8700600000 -0.1125080000 C 2.9523140000 1.8195230000 1.0548120000 C 0.9554050000 2.0854230000 1.2137160000 C 2.2485750000 0.6107980000 1.2159940000 C 1.8106830000 3.1535780000 1.5269850000 H 4.9949670000 -1.5217040000 -1.8758850000 C 2.2576560000 4.0167770000 0.5151190000 H 4.5363630000 2.8657830000 0.0140470000 C 1.8391530000 3.8118510000 -0.8102740000 H 2.6888880000 2.6765220000 1.6660770000 C 0.9798620000 2.7485930000 -1.1192570000 H 1.6868170000 0.4494880000 2.1308300000 H 0.5979570000 1.4178920000 1.9932480000 C 0.5221760000 -1.7060320000 1.1183690000 H 2.1855490000 4.4740150000 -1.5971870000 H 0.0277530000 -2.6770320000 1.0192110000 H 0.6649720000 2.5838780000 -2.1468340000 C -0.3440030000 -0.5704310000 0.5623620000 H 2.1254750000 3.3102240000 2.5536670000 C 0.1342420000 0.6681890000 0.5028350000 H 2.9223070000 4.8401870000 0.7549720000 C -0.3060870000 2.0011260000 0.1780660000 C -4.9079300000 -0.8221050000 0.5452120000 C -1.3775870000 2.6036830000 0.8822940000 C -3.1322160000 -2.4310790000 0.1653230000 C 0.3549260000 2.7389360000 -0.8324880000 C -4.4477980000 -2.1402890000 0.5622810000 C -1.7970850000 3.8986600000 0.5548050000 C -4.0649380000 0.2346300000 0.1242840000 H -1.8631140000 2.0492510000 1.6813960000 H -5.5183880000 1.8237140000 0.5042740000 C -0.0757420000 4.0288910000 -1.1591480000 H -5.9176090000 -0.5896940000 0.8723390000 H 1.1922630000 2.2833970000 -1.3536170000 H -1.8394880000 0.9541220000 -1.9377110000 C -1.1531820000 4.6133220000 -0.4702980000 Sn 2.1212850000 -1.1570130000 0.0209280000 H -2.6224210000 4.3512560000 1.0951200000 C 2.3241220000 -1.5544510000 2.1003970000 H 0.4277600000 4.5810200000 -1.9460700000 H 2.2907260000 -0.6251700000 2.6798590000 H -1.4816400000 5.6159480000 -0.7234870000 H 1.5081490000 -2.2044530000 2.4333470000 Sn -2.2850400000 -1.0008840000 -0.2563400000 H 3.2760040000 -2.0555540000 2.3087780000 C -2.1738610000 -3.0280500000 -0.9128720000 C 3.4812670000 0.3554400000 -0.6122710000 H -3.0236640000 -3.2731170000 -1.5599260000 H 4.5086790000 -0.0255670000 -0.5617330000 H -1.2526310000 -3.1955870000 -1.4834230000 H 3.2726420000 0.6442420000 -1.6491010000 H -2.1870180000 -3.7194330000 -0.0624870000 H 3.4096750000 1.2545380000 0.0100980000 C -3.7799550000 -0.7916190000 1.2462170000 C 2.5168420000 -2.8996760000 -1.1355340000 H -4.7263890000 -1.2359140000 0.9176910000 H 3.5719030000 -3.1844160000 -1.0481810000 H -3.4683640000 -1.2864480000 2.1722040000 H 1.8951440000 -3.7317000000 -0.7928020000 H -3.9559310000 0.2676760000 1.4638560000 H 2.3029760000 -2.7209790000 -2.1960440000 C -2.6307470000 0.3370360000 -1.8693540000 H -1.6119110000 3.2380650000 -0.6466920000 H -3.5200970000 0.0436990000 -2.4385940000 H -3.9085460000 3.6837160000 0.0908840000 H -2.7766600000 1.3565340000 -1.4952190000 H -0.8296320000 -1.9451640000 -1.7644500000 H -1.7704210000 0.3461340000 -2.5475470000 H -2.7489050000 -3.4442910000 0.2051140000 H 1.6577990000 -3.7396280000 -0.2865230000 H -5.1011080000 -2.9402970000 0.8939640000 H 3.7181160000 -3.6432400000 -1.6931440000 F -0.4147250000 -2.8725510000 -0.0067710000 F 0.6706210000 -1.5153990000 2.5590460000

(14c-t) nap_P_trans_F (14c) nap_P_cis_F E = -954.2742513 E = -954.2770144 No. of Negative Frequencies = 0 No. of Negative Frequencies = 0

168

C -4.6747790000 -1.9828820000 0.5202460000 C -3.3337820000 -2.3232860000 0.2852370000 C -5.0660810000 -0.6428860000 0.4759780000 C -2.3977030000 -1.3245290000 -0.0308070000 C -2.7863890000 0.0173460000 -0.1089220000 C -4.1313150000 0.3777850000 0.1792460000 C 1.1331540000 -3.6475050000 -1.4845080000 C -4.5038250000 1.7710810000 0.2427070000 C 0.2832000000 -2.9038940000 -0.6198790000 H -5.5380130000 2.0298590000 0.4487320000 C 2.4776930000 -3.3522150000 -1.5467470000 C -3.5100600000 2.7736760000 0.1698000000 C 0.7791000000 -1.8967950000 0.1910900000 C -2.1946530000 2.4695760000 -0.1176940000 C 2.1779590000 -1.5563320000 0.1371450000 C -1.7808910000 1.0751340000 -0.5321100000 C 3.0238690000 -2.2995050000 -0.7517510000 H -6.0949590000 -0.3667160000 0.6901090000 C 4.4099020000 -1.9703580000 -0.8538100000 H -3.7848090000 3.8055440000 0.3665410000 H 5.0319430000 -2.5522320000 -1.5287330000 H -1.4426780000 3.2516360000 -0.1342600000 C 4.9470220000 -0.9316560000 -0.1205350000 H -1.7925990000 1.0685080000 -1.6443400000 C 4.1116580000 -0.1860050000 0.7591590000 C -0.9670260000 -1.6991850000 -0.2903460000 C 2.7703590000 -0.4932310000 0.8926790000 H -0.7164910000 -2.6274040000 0.2343040000 H 3.1394830000 -3.9045880000 -2.2083450000 C 0.0467240000 -0.6057110000 -0.0389840000 H 5.9993020000 -0.6815790000 -0.2079050000 C -0.3397330000 0.6875360000 -0.1675070000 H 4.5339220000 0.6309340000 1.3349530000 C 0.6637180000 1.7869410000 -0.0543050000 H 2.1581220000 0.0619480000 1.5895690000 C 0.9356220000 2.6314720000 -1.1484890000 C -0.2142120000 -1.0812470000 1.0174870000 C 1.3845420000 1.9640640000 1.1402360000 C -0.4292260000 -0.0117830000 3.2051630000 C 1.9317640000 3.6121980000 -1.0584280000 H -1.5102050000 -0.1428570000 3.0728400000 H 0.3864070000 2.4989520000 -2.0771950000 H -0.1392370000 -0.2729360000 4.2233790000 C 2.3800940000 2.9490680000 1.2338660000 H -0.1620880000 1.0286630000 2.9933880000 H 1.1534070000 1.3340190000 1.9949240000 O 0.3136360000 -0.9150040000 2.3391060000 C 2.6606480000 3.7715200000 0.1326950000 C -0.5653620000 0.2286250000 0.2895970000 H 2.1460820000 4.2444330000 -1.9139420000 C 0.2128960000 1.2754150000 0.2335410000 H 2.9288250000 3.0744140000 2.1618350000 C 0.8783900000 2.4846800000 0.0456740000 H 3.4328610000 4.5306730000 0.2015280000 C 0.6361930000 3.6064880000 0.9028210000 Sn 2.0945980000 -1.2326890000 0.1030460000 C 1.8512640000 2.6261750000 -0.9961490000 C 2.8673110000 -1.0325880000 2.0839270000 C 1.3254040000 4.8029530000 0.7128660000 H 2.0753860000 -1.1618100000 2.8305440000 H -0.0992530000 3.5128080000 1.6964950000 H 3.6387120000 -1.7892830000 2.2684320000 C 2.5279800000 3.8317060000 -1.1689950000 H 3.3157930000 -0.0419370000 2.2199360000 H 2.0573560000 1.7744150000 -1.6367330000 C 2.0342980000 -3.3021210000 -0.4027740000 C 2.2742660000 4.9297220000 -0.3214820000 H 1.6941940000 -3.9035380000 0.4488260000 H 1.1261270000 5.6455120000 1.3675720000 H 1.3486730000 -3.4671300000 -1.2415190000 H 3.2616640000 3.9226880000 -1.9636110000 H 3.0283610000 -3.6609860000 -0.6925340000 H 2.8064790000 5.8641550000 -0.4630890000 C 3.2772160000 -0.1038840000 -1.2558160000 Sn -2.5349320000 0.2328070000 -0.6026040000 H 4.2625730000 -0.5636220000 -1.3933430000 C -2.8697210000 -1.4538310000 -1.8543660000 H 2.7826960000 -0.0421540000 -2.2314580000 H -3.7047810000 -1.2702820000 -2.5401200000 H 3.4154850000 0.9160790000 -0.8761650000 H -1.9763050000 -1.6769440000 -2.4479090000 H -3.0132040000 -3.3602200000 0.3338410000 H -3.1043040000 -2.3255930000 -1.2342580000 H -5.4007230000 -2.7556920000 0.7490520000 C -4.0037060000 0.3865350000 0.9303460000 F -0.8366710000 -2.0667940000 -1.7158510000 H -4.9989650000 0.5705940000 0.5098380000 H -4.0261270000 -0.5465260000 1.5028510000 H -3.7628020000 1.2107180000 1.6116520000 (15a) nap_SM_OMe2 C -2.5192680000 2.0215460000 -1.7628710000 E = -1083.9661702 H -3.4936010000 2.2043610000 -2.2308370000 No. of Negative Frequencies = 0 H -2.2720820000 2.8846530000 -1.1330520000 H -1.7628200000 1.9586960000 -2.5538000000 H -0.7790640000 -3.1233960000 -0.6023130000 H 0.7106820000 -4.4373740000 -2.0964250000 O -1.5020860000 -1.7492340000 1.1128010000 C -1.5566910000 -2.9166880000 1.9794210000 H -1.5682520000 -2.6123740000 3.0300240000 H -2.4845770000 -3.4324110000 1.7268830000 H -0.6991400000 -3.5742750000 1.8072650000

169 O -1.4832410000 -2.1567150000 0.5096360000 (15b) nap_TS_OMe2 C -1.7177550000 -3.4455890000 1.1451000000 E = -1083.950005 H -2.1604810000 -3.3042720000 2.1360540000 No. of Negative Frequencies = 1 H -2.4142910000 -3.9810940000 0.4973770000 freq = -438.7374 H -0.7860510000 -4.0087290000 1.2517140000

(15c) nap_P_OMe2 E = -1083.989036 No. of Negative Frequencies = 0

C 1.8936010000 -3.5212100000 -1.6388060000 C 0.8006060000 -3.1242640000 -0.8239230000 C 3.0979680000 -2.8434440000 -1.5644860000 C 0.9543210000 -2.1119060000 0.1125030000 C 2.2010470000 -1.4323750000 0.2382750000 C 3.9986290000 -1.7296880000 -1.4131090000 C 3.2646560000 -1.7599610000 -0.6524560000 C 2.7738740000 -2.0783450000 -0.8112680000 C 4.4588440000 -0.9687380000 -0.6475050000 C 4.5219160000 -0.4473040000 -1.2501240000 H 5.2648530000 -1.2337080000 -1.3261320000 C 2.1013430000 -1.1372130000 -0.0251600000 C 4.5787430000 0.1229920000 0.2029500000 C 2.6026680000 0.1637410000 0.1209300000 C 3.5458060000 0.4399660000 1.1145020000 C 3.8223760000 0.5302810000 -0.4969520000 C 2.3487300000 -0.3057770000 1.1400510000 C 4.2987100000 1.8893050000 -0.3912150000 H 3.9213470000 -3.1057610000 -2.2232450000 H 5.2484890000 2.1527620000 -0.8465620000 H 5.4858670000 0.7191890000 0.1961960000 C 3.5141470000 2.8715680000 0.2559130000 H 3.6792300000 1.2555840000 1.8177610000 C 2.2942710000 2.5715290000 0.8320380000 H 1.7446980000 -0.2877600000 2.0400870000 C 1.7562580000 1.1669570000 0.8895530000 C -0.2348710000 -1.5031080000 0.8319110000 H 5.4596700000 -0.1735630000 -1.7258380000 C -0.9330860000 -0.8519580000 3.0863380000 H 3.8770350000 3.8944070000 0.2931120000 H -1.9676790000 -0.9772590000 2.7436620000 H 1.7132260000 3.3500590000 1.3174820000 H -0.8200710000 -1.2527250000 4.0939800000 H 1.7779070000 0.8489920000 1.9498640000 H -0.6771160000 0.2137170000 3.0730280000 C 0.7695400000 -1.3927560000 0.6562600000 O -0.0129790000 -1.6115290000 2.2538380000 C -0.0897830000 -1.4478720000 2.9582250000 C -0.4223030000 -0.0519310000 0.3463730000 H -0.8685980000 -2.1338590000 2.6030400000 C 0.5793810000 0.8129170000 0.4173340000 H 0.2755500000 -1.7702070000 3.9337860000 C 0.8630540000 2.2116690000 0.2210720000 H -0.5069960000 -0.4368240000 3.0286540000 C 0.1868100000 3.1964960000 0.9815860000 O 1.0664410000 -1.4689910000 2.0768700000 C 1.8625840000 2.6192830000 -0.6939160000 C -0.2123050000 -0.2686680000 0.3268300000 C 0.4820020000 4.5529710000 0.8066560000 C 0.2658140000 0.9891040000 0.4774630000 H -0.5712640000 2.8841130000 1.6954560000 C -0.5794250000 2.2006740000 0.2905380000 C 2.1460490000 3.9779460000 -0.8702740000 C -1.6917470000 2.4227320000 1.1220550000 H 2.3981160000 1.8618140000 -1.2593600000 C -0.2865710000 3.1358420000 -0.7224920000 C 1.4587940000 4.9500280000 -0.1224810000 C -2.5047970000 3.5525590000 0.9428540000 H -0.0492030000 5.3006160000 1.3870120000 H -1.9154330000 1.7058240000 1.9083560000 H 2.9040980000 4.2810800000 -1.5853560000 C -1.1048450000 4.2569500000 -0.9117090000 H 1.6839330000 6.0025940000 -0.2596000000 H 0.5724750000 2.9704040000 -1.3667790000 Sn -2.3245880000 0.3030120000 -0.5976650000 C -2.2162250000 4.4698180000 -0.0777070000 C -2.5892610000 -1.0429340000 -2.2223770000 H -3.3609650000 3.7109790000 1.5907760000 H -3.1156850000 -0.5709310000 -3.0593790000 H -0.8798320000 4.9612730000 -1.7060550000 H -1.6111380000 -1.3915630000 -2.5720130000 H -2.8479820000 5.3399370000 -0.2236880000 H -3.1582870000 -1.9146170000 -1.8828350000 Sn -2.0455200000 -0.9670400000 -0.5418680000 C -3.8883550000 0.1306940000 0.8406800000 C -1.5763260000 -2.0997570000 -2.2807760000 H -4.8480860000 0.4488770000 0.4175930000 H -2.3056630000 -1.9349980000 -3.0817520000 H -3.9718880000 -0.9150880000 1.1571120000 H -0.5810130000 -1.8201070000 -2.6441470000 H -3.6816510000 0.7508910000 1.7211200000 H -1.5518890000 -3.1640600000 -2.0249820000 C -2.2564050000 2.3036150000 -1.3381450000 C -3.1353780000 -2.1292250000 0.8765980000 H -3.0472630000 2.4580690000 -2.0826100000 H -4.1278650000 -2.3796740000 0.4842570000 H -2.3911710000 3.0355320000 -0.5339980000 H -2.5954330000 -3.0610280000 1.0805800000 H -1.2891780000 2.5073120000 -1.8132620000 H -3.2703750000 -1.5847200000 1.8190330000 H -0.1717630000 -3.5824160000 -0.9710360000 C -3.2873530000 0.6603420000 -1.1496160000 H 1.7635400000 -4.3303920000 -2.3496320000 H -4.0084660000 0.3002370000 -1.8946720000

170 H -3.8431550000 1.0809400000 -0.3047830000 H 1.1698510000 -3.3617690000 0.4106880000 H -2.6994370000 1.4693130000 -1.5995420000 H 3.1426510000 -3.9663590000 -0.9796640000 H 2.3439100000 -3.0592530000 -0.9794800000 F 0.7685880000 -0.3293480000 2.6000270000 H 4.5287890000 -2.4592220000 -2.0163230000 F -0.1863760000 -2.1816620000 1.7699050000 O 0.1266400000 -2.6162090000 0.2430090000 C 0.6379320000 -3.8595710000 0.8027890000 H 0.0283380000 -4.1538900000 1.6635420000 (16b) nap_TS_F2 H 0.5567230000 -4.6139530000 0.0175920000 E = -1053.461299 H 1.6760320000 -3.7521790000 1.1273700000 No. of Negative Frequencies = 1 freq = -441.7685

(16a) nap_SM_F2 E = -1053.476019 No. of Negative Frequencies = 0

C 3.1692780000 -3.0275770000 -1.1320950000 C 1.9620780000 -2.9574720000 -0.3871460000 C 3.0244190000 -2.9433740000 -0.6401840000 C 4.0229920000 -1.9383240000 -1.1786030000 C 1.8960230000 -2.5992740000 0.1559410000 C 1.6773010000 -1.8202020000 0.3519690000 C 3.9484160000 -1.9781080000 -0.9785420000 C 2.5782900000 -0.7205150000 0.3896890000 C 1.7180100000 -1.3055530000 0.6099570000 C 3.7346880000 -0.7513240000 -0.4421430000 C 2.6772030000 -0.2801680000 0.2982360000 C 4.5585140000 0.4155060000 -0.5395290000 C 3.7971360000 -0.6333110000 -0.5218990000 H 5.4386310000 0.3847590000 -1.1755640000 C 4.7554850000 0.3638960000 -0.8755990000 C 4.2329440000 1.5678690000 0.1643250000 H 5.5985930000 0.0759970000 -1.4975580000 C 3.1213570000 1.5886930000 1.0394550000 C 4.6161770000 1.6656780000 -0.4370640000 C 2.2780570000 0.4668160000 1.1633200000 C 3.5136410000 2.0166780000 0.3932400000 H 4.9181080000 -1.9672870000 -1.7938680000 C 2.5736250000 1.0708510000 0.7594340000 H 4.8600150000 2.4497010000 0.0804770000 H 4.8078990000 -2.2254610000 -1.5954730000 H 2.9257520000 2.4700250000 1.6415020000 H 5.3460950000 2.4200220000 -0.7110530000 H 1.6789930000 0.3708400000 2.0641670000 H 3.4151000000 3.0359030000 0.7518320000 C 0.3256200000 -1.6023030000 0.9713550000 H 1.7666570000 1.3563730000 1.4230300000 C -0.4095130000 -0.3824070000 0.4367270000 C 0.4543810000 -0.9664260000 1.3717540000 C 0.2188730000 0.7855100000 0.3920500000 C -0.5730390000 -0.1733690000 0.5855080000 C -0.0207330000 2.1787300000 0.1208440000 C -0.5621750000 1.1323070000 0.5007960000 C -0.9150790000 2.9256510000 0.9254520000 C -0.8090130000 2.4720150000 0.2022400000 C 0.6937060000 2.8368940000 -0.9082530000 C -1.6945990000 3.2579460000 1.0058290000 C -1.1168400000 4.2879550000 0.6774790000 C -0.1509790000 3.1004040000 -0.9030730000 H -1.4421810000 2.4266720000 1.7341670000 C -1.9183120000 4.5990320000 0.6991040000 C 0.4778990000 4.1966250000 -1.1569000000 H -2.1845260000 2.7932990000 1.8553980000 H 1.4040540000 2.2695100000 -1.5029840000 C -0.3902290000 4.4428320000 -1.1918410000 C -0.4284400000 4.9268480000 -0.3682450000 H 0.5381070000 2.5146670000 -1.5037290000 H -1.8101300000 4.8515010000 1.2933800000 C -1.2736500000 5.2028090000 -0.3991750000 H 1.0173340000 4.6896810000 -1.9591190000 H -2.5954950000 5.1827150000 1.3142310000 H -0.5906650000 5.9820860000 -0.5614430000 H 0.1115860000 4.9056960000 -2.0354160000 Sn -2.4207210000 -0.6932400000 -0.2960040000 H -1.4534640000 6.2471180000 -0.6303350000 C -2.3336560000 -2.1788790000 -1.8133650000 Sn -2.1475800000 -1.2836860000 -0.4100410000 H -3.2605480000 -2.2008560000 -2.3973980000 C -1.3144760000 -2.9897740000 -1.3691090000 H -1.5003400000 -1.9805630000 -2.4963590000 H -2.0180570000 -3.4006470000 -2.1020910000 H -2.1796200000 -3.1618410000 -1.3574310000 H -0.3839710000 -2.7331020000 -1.8867120000 C -3.6241900000 -1.3044810000 1.3450510000 H -1.0973900000 -3.7639550000 -0.6252740000 H -4.6615190000 -1.4693570000 1.0331760000 C -3.5775960000 -1.8459040000 1.0550390000 H -3.2321050000 -2.2369290000 1.7638240000 H -4.3990390000 -2.4170290000 0.6084340000 H -3.6165170000 -0.5440520000 2.1334000000 H -3.0947720000 -2.4635050000 1.8190670000 C -3.0796440000 1.1631270000 -1.0980410000 H -3.9973640000 -0.9596160000 1.5422720000 H -3.9791900000 1.0089410000 -1.7060420000 C -2.9310110000 0.1226650000 -1.7950670000 H -3.3166980000 1.8768020000 -0.3022340000 H -3.7659380000 -0.3011390000 -2.3640650000 H -2.3070190000 1.6146700000 -1.7307590000 H -3.2894130000 1.0168020000 -1.2721690000 H 1.2508100000 -3.7746590000 -0.4162560000 H -2.1546410000 0.4362750000 -2.5018810000 H 3.3975530000 -3.9262060000 -1.6946470000

171 F 0.4205070000 -1.5232550000 2.3965820000 No. of Negative Frequencies = 1 F -0.4982490000 -2.7447300000 0.7622900000 freq = -543.2664

(16c) nap_P_F2 E = -1053.506661 No. of Negative Frequencies = 0

C -2.22268 2.35433 -1.41575 C -1.42201 1.19006 -1.70382 C -3.28993 2.25806 -0.56001 C -1.79573 -0.08012 -1.16710 C -2.85680 -0.17303 -0.21851 C 4.7021280000 -1.8331750000 -0.3103830000 C -3.63770 1.00619 0.05495 C 3.3550350000 -2.1844850000 -0.1516410000 C -4.73581 0.93132 0.95374 C 5.0781750000 -0.4862040000 -0.2903180000 C -5.05507 -0.25338 1.59717 C 2.3989900000 -1.1778170000 0.0683670000 C -4.25843 -1.40951 1.37191 C 2.7627960000 0.1681990000 0.1359320000 C -3.18805 -1.37287 0.49552 C 4.1199630000 0.5335590000 -0.0876900000 H -3.89757 3.13017 -0.33336 C 4.4741110000 1.9290200000 -0.1974860000 H -2.56286 -2.24622 0.36957 H 5.5148540000 2.1958850000 -0.3527240000 C -0.62048 -1.03176 -1.33987 C 3.4610240000 2.9140810000 -0.2569190000 C 0.53052 -0.29505 -0.62872 C 2.1365620000 2.6027490000 -0.0237390000 C 0.39914 1.02975 -0.63124 C 1.7425270000 1.2353240000 0.4918360000 C 1.05743 2.25162 -0.24040 H 6.1150990000 -0.2065180000 -0.4538710000 C 2.23616 2.68483 -0.89536 H 3.7300150000 3.9337250000 -0.5144830000 C 0.49599 3.06900 0.77073 H 1.3659180000 3.3612990000 -0.1093960000 C 2.84910 3.88831 -0.52810 H 1.7767000000 1.3165170000 1.6010260000 H 2.66187 2.06477 -1.67891 C 0.9598630000 -1.5534810000 0.2398140000 C 1.11605 4.26967 1.13425 C -0.0771060000 -0.4839110000 0.0914850000 H -0.41870 2.74557 1.25895 C 0.3006810000 0.8123850000 0.1877180000 C 2.29440 4.68421 0.48886 C -0.7126150000 1.9021470000 0.0742920000 H 3.75867 4.20474 -1.02851 C -0.9673250000 2.7679200000 1.1544740000 H 0.68342 4.88289 1.91818 C -1.4354610000 2.0648110000 -1.1212600000 H 2.77228 5.61598 0.77306 C -1.9522280000 3.7591240000 1.0512870000 Sn 2.00257 -1.47711 0.36851 H -0.4123900000 2.6484910000 2.0815370000 C 1.11880 -2.36622 2.08412 C -2.4167870000 3.0623420000 -1.2287920000 H 1.81483 -3.04906 2.58424 H -1.2170710000 1.4155230000 -1.9648570000 H 0.81033 -1.59764 2.80083 C -2.6821420000 3.9073930000 -0.1405510000 H 0.23137 -2.92409 1.76940 H -2.1547790000 4.4092250000 1.8960220000 C 2.71161 -2.95586 -0.99093 H -2.9683600000 3.1786280000 -2.1560780000 H 3.48704 -3.57746 -0.52923 H -3.4446020000 4.6751910000 -0.2194330000 H 1.87729 -3.60113 -1.28685 Sn -2.1171770000 -1.1832540000 -0.0523830000 H 3.13357 -2.49287 -1.88987 C -2.7478010000 -1.1133180000 -2.0872290000 C 3.57930 -0.16067 0.93830 H -3.4827750000 -1.9013970000 -2.2858560000 H 3.17870 0.70383 1.48078 H -3.2076260000 -0.1459470000 -2.3186630000 H 4.30049 -0.67237 1.58635 H -1.8930890000 -1.2670870000 -2.7553320000 H 4.11260 0.21563 0.05790 C -2.1757010000 -3.1755500000 0.6749810000 H -0.81209 1.21431 -2.60694 H -3.2100910000 -3.5335980000 0.7341210000 H -1.96476 3.30087 -1.87930 H -1.6073210000 -3.8352760000 0.0125400000 H -4.48717 -2.32787 1.90322 H -1.7246420000 -3.2318570000 1.6706330000 O -0.71707 -2.36720 -0.80426 C -3.3312590000 0.0731840000 1.1638230000 C -1.42172 -3.28957 -1.67250 H -4.3039260000 -0.4001450000 1.3431250000 H -0.89701 -3.38785 -2.63171 H -2.8493610000 0.2460940000 2.1328890000 H -1.43619 -4.25268 -1.16112 H -3.4981010000 1.0457550000 0.6863990000 H -2.44996 -2.95046 -1.85386 H 3.0371010000 -3.2198680000 -0.2018780000 H -0.37743 -1.11257 -2.41516 H 5.4482010000 -2.6040620000 -0.4681750000 H -5.31955 1.83001 1.13548 F 0.7847910000 -2.1907980000 1.5203650000 H -5.89545 -0.29913 2.28182 F 0.6468210000 -2.6162740000 -0.6721850000

(17b-t) nap_TS_trans_5 (17b) nap_TS_cis_5 E = -969.4575208 E = -969.4598829 No. of Negative Frequencies = 1

172 freq = -493.7275

C 2.4535520000 2.1760090000 1.3067300000 C 1.6209430000 1.0404750000 1.6110920000 C 4.1742480000 -1.3010200000 -0.3318000000 C 3.5191130000 2.0433700000 0.4482790000 C 3.4344970000 -0.0857620000 -0.2618970000 C 1.9550880000 -0.2311700000 1.0753260000 C 2.0357270000 -0.0178900000 -0.4776530000 C 3.0641180000 -0.3839450000 0.1982860000 C 3.3567470000 2.3480290000 0.3342610000 C 3.8611800000 0.7693290000 -0.1185720000 C 2.0325790000 2.4353890000 0.0785500000 C 4.9721120000 0.6329070000 -0.9952640000 C 1.3214550000 1.2995820000 -0.6193580000 H 5.5645170000 1.5147040000 -1.2255720000 C 1.0320480000 -1.1419480000 -0.3553240000 C 5.2989650000 -0.5935800000 -1.5496820000 C -0.3041700000 -0.4066650000 -0.1512990000 C 4.5162880000 -1.7410480000 -1.2367720000 C -0.1083720000 0.9377730000 -0.2105790000 C 3.4284050000 -1.6386410000 -0.3888230000 C -1.1292440000 1.9856480000 0.0036160000 H 4.1372650000 2.9021100000 0.1991090000 C -2.0007580000 1.9153280000 1.1090790000 H 6.1494290000 -0.6863010000 -2.2168380000 C -2.9915350000 2.8884640000 1.3013230000 H 4.7824630000 -2.7026650000 -1.6635820000 C -3.1197430000 3.9509430000 0.3929930000 H 2.8578930000 -2.5287510000 -0.1448250000 C -2.2388380000 4.0437430000 -0.6972170000 C 0.8035210000 -1.2043450000 1.1498670000 C -1.2452530000 3.0740490000 -0.8841620000 H 0.9881420000 -2.1518880000 0.6263090000 H 0.9975180000 -1.7997560000 -1.2451260000 C -0.6504120000 -2.2845310000 2.7758910000 H -1.8750060000 1.1118050000 1.8308020000 H -0.6684030000 -3.1716580000 2.1223290000 H -2.3283730000 4.8677800000 -1.3975680000 H -0.6162840000 -2.6072920000 3.8170680000 H -0.5724540000 3.1478700000 -1.7347040000 H -1.5590860000 -1.6925360000 2.6060010000 H -3.6533080000 2.8235730000 2.1591210000 O 0.5370890000 -1.4945160000 2.5506810000 H -3.8872680000 4.7039720000 0.5388180000 C -0.3687670000 -0.4295860000 0.4903570000 C 5.5210880000 1.0948180000 0.2670690000 C -0.2347380000 0.8968940000 0.5298820000 C 5.5548550000 -1.3028400000 -0.1511680000 C -0.9546520000 2.1033590000 0.2022860000 C 4.1309130000 1.1259720000 0.0771000000 C -2.1501460000 2.4292610000 0.8886690000 H 3.8867010000 3.1873600000 0.7786760000 C -0.4613020000 2.9962150000 -0.7785980000 O 1.4331090000 -1.9661100000 0.7808280000 C -2.8473740000 3.6029330000 0.5780420000 C 0.6885260000 -3.1894190000 0.9538250000 H -2.5167270000 1.7559670000 1.6587950000 H 1.2597950000 -3.8021590000 1.6528540000 C -1.1668920000 4.1643670000 -1.0874000000 H -0.3076390000 -3.0041300000 1.3811590000 H 0.4669280000 2.7557910000 -1.2884250000 H 0.5760680000 -3.7273660000 0.0009740000 C -2.3624390000 4.4718790000 -0.4139230000 H 6.1092130000 -2.2329430000 -0.2251000000 H -3.7659690000 3.8399160000 1.1050810000 Sn -2.2308080000 -1.3283720000 -0.1400770000 H -0.7870910000 4.8370470000 -1.8495280000 C -2.9521180000 -1.6033950000 1.8506770000 H -2.9052910000 5.3797900000 -0.6550620000 H -2.1327890000 -1.5186380000 2.5738340000 Sn -1.9682240000 -1.3507900000 -0.5920320000 H -3.7019940000 -0.8397030000 2.0887610000 C -1.1898080000 -3.1909770000 -1.3403990000 H -3.4171760000 -2.5884920000 1.9694430000 H -1.8972230000 -3.6579610000 -2.0349650000 C -2.0501970000 -3.2208140000 -1.1168990000 H -0.2487060000 -3.0186540000 -1.8753640000 H -1.1940810000 -3.2353160000 -1.8017300000 H -0.9972840000 -3.8986010000 -0.5252960000 H -1.9243820000 -4.0329920000 -0.3924090000 C -3.6558900000 -1.7354260000 0.6553200000 H -2.9542690000 -3.4222640000 -1.7029850000 H -3.8628190000 -0.8753570000 1.3025250000 C -3.5686170000 -0.1228130000 -1.2751690000 H -4.5438130000 -1.9191470000 0.0393960000 H -3.8743460000 0.7676470000 -0.7154750000 H -3.4915820000 -2.6148850000 1.2878130000 H -3.0838920000 0.2094430000 -2.2005910000 C -2.5108800000 -0.0304490000 -2.1649430000 H -4.4653700000 -0.6949330000 -1.5413660000 H -2.9261730000 0.8988350000 -1.7583020000 H 1.4676280000 3.3368150000 0.3032180000 H -1.6302600000 0.2287450000 -2.7631750000 H 1.2784340000 1.5775200000 -1.6949650000 H -3.2576640000 -0.4868230000 -2.8246700000 C 6.2391150000 -0.1014750000 0.1383630000 H 0.9815730000 1.0783790000 2.4896050000 H 3.6407670000 -2.2250740000 -0.5272120000 H 2.2207580000 3.1370720000 1.7537990000 H 7.3146140000 -0.1095450000 0.2808050000 H 6.0394410000 2.0128090000 0.5319940000

(17c) nap_P_cis_5 E = -969.4968363 (17c-t) nap_P_trans_5 No. of Negative Frequencies = 0 E = -969.4978370 No. of Negative Frequencies = 0

173 freq = -538.9404

C 1.5062510000 2.0816580000 1.8438570000 C 0.5405960000 1.0322260000 1.9923520000 C -1.0581310000 -1.1957250000 0.4790650000 C 2.6930620000 1.8449950000 1.1833690000 H -1.2774540000 -1.8951880000 -0.3448950000 C 0.8630760000 -0.2799580000 1.5121890000 C 0.2687540000 -0.4456990000 0.2651640000 C 2.0469210000 -0.5000630000 0.7697530000 C 0.0888390000 0.8796630000 0.5016310000 C 3.0067050000 0.5613870000 0.6418400000 C 1.1427690000 1.9198420000 0.4014720000 C 4.2669400000 0.3199080000 -0.0498990000 C 2.2967000000 1.8516770000 1.2066120000 C 4.5035730000 -0.9513630000 -0.6480810000 C 1.0341280000 2.9551820000 -0.5485280000 C 3.4850200000 -1.9696420000 -0.5700090000 C 3.3265430000 2.7937000000 1.0584720000 C 2.3174970000 -1.7618180000 0.1025770000 H 2.3765440000 1.0642260000 1.9519380000 H 3.4003580000 2.6594180000 1.0816460000 C 2.0640620000 3.8927230000 -0.7006700000 H 1.5480650000 -2.5210680000 0.1095640000 H 0.1579140000 2.9985090000 -1.1892750000 C -0.4236840000 -1.0957360000 1.5027640000 C 3.2145340000 3.8141850000 0.1016880000 C -1.3692020000 -0.2436220000 0.6364860000 H 4.2101090000 2.7312350000 1.6858010000 C -1.0929950000 1.0589130000 0.6717690000 H 1.9750020000 4.6753640000 -1.4471560000 C -1.5722480000 2.3405510000 0.2129350000 H 4.0121860000 4.5401580000 -0.0174090000 C -2.8204580000 2.8456970000 0.6506820000 C -2.0625180000 -0.0763590000 0.5713180000 C -0.7704340000 3.1383020000 -0.6383100000 C -1.3523390000 1.1972150000 0.9484360000 C -3.2650140000 4.1022470000 0.2234370000 C -3.4035460000 -0.1032590000 0.1206450000 H -3.4310310000 2.2402520000 1.3143890000 C -2.0426510000 2.4398580000 0.4430860000 C -1.2222350000 4.3928020000 -1.0632620000 H -1.3041300000 1.2881210000 2.0525190000 H 0.1952380000 2.7572380000 -0.9579890000 C -4.0625150000 1.1416750000 -0.1618230000 C -2.4703330000 4.8792580000 -0.6366530000 C -3.3102550000 2.3943120000 -0.0260620000 H -4.2286910000 4.4747030000 0.5557680000 H -1.5239100000 3.3889820000 0.5500820000 H -0.6045950000 4.9920810000 -1.7244520000 H -3.8125800000 3.3107990000 -0.3272890000 H -2.8177890000 5.8522650000 -0.9681000000 C -6.0712730000 -0.0732940000 -0.8278740000 Sn -2.7899080000 -1.2778920000 -0.5779700000 C -5.4239850000 -1.3014070000 -0.5667610000 C -1.7558050000 -2.2715930000 -2.1462120000 C -4.1105730000 -1.3197560000 -0.1037580000 H -2.4493710000 -2.8118610000 -2.8004890000 C -5.3851060000 1.1330140000 -0.6283440000 H -1.1952790000 -1.5518630000 -2.7524080000 H -7.0950640000 -0.0647240000 -1.1864300000 H -1.0468940000 -2.9819410000 -1.7093290000 H -5.9571790000 -2.2339140000 -0.7209080000 C -3.8506690000 -2.6616010000 0.6461680000 Sn 2.0814560000 -1.2759620000 -0.4887110000 H -4.6197630000 -3.1884960000 0.0702210000 C 2.8633880000 0.0324120000 -1.9726500000 H -3.1473490000 -3.3997450000 1.0467210000 H 2.0867700000 0.3000210000 -2.6979240000 H -4.3397380000 -2.1517680000 1.4837910000 H 3.2291270000 0.9571140000 -1.5102510000 C -4.1204520000 0.1819010000 -1.3791410000 H 3.6929860000 -0.4409050000 -2.5107700000 H -3.5588740000 1.0196620000 -1.8090650000 C 3.5183370000 -1.5439970000 1.0695270000 H -4.7469470000 -0.2548070000 -2.1659120000 H 4.1980840000 -0.6842590000 1.0992050000 H -4.7777680000 0.5840130000 -0.5999670000 H 3.0305550000 -1.6306520000 2.0474540000 H -0.1911620000 1.1310280000 2.7946290000 H 4.1135090000 -2.4486000000 0.8998640000 H 1.2935400000 3.0630480000 2.2552560000 C 1.6170610000 -3.1752670000 -1.3457980000 C 5.7228770000 -1.2038050000 -1.3270220000 H 0.6431480000 -3.1619800000 -1.8488530000 C 5.2899780000 1.3038410000 -0.1571040000 H 2.3765370000 -3.4460330000 -2.0885580000 H 5.1556440000 2.2812470000 0.2912340000 H 1.5985280000 -3.9572380000 -0.5782930000 C 6.7038580000 -0.2270280000 -1.4171320000 H -3.6202730000 -2.2612170000 0.1268160000 H 7.6351220000 -0.4264250000 -1.9365300000 H -5.8749880000 2.0784030000 -0.8472740000 C 6.4800810000 1.0390790000 -0.8220790000 O -1.0972220000 -1.9564240000 1.7311980000 H 7.2444500000 1.8067320000 -0.8863840000 C -0.2318540000 -3.1127960000 1.7471950000 H 5.8757340000 -2.1812020000 -1.7768310000 H -0.4926300000 -3.6840630000 2.6389230000 H 3.6663980000 -2.9153720000 -1.0738420000 H -0.3888360000 -3.7347660000 0.8530600000 O -0.4100330000 -2.4412770000 0.9852100000 H 0.8287980000 -2.8272820000 1.8033220000 C 0.0296590000 -3.4317130000 1.9481470000 H -0.6359760000 -3.4379260000 2.8210200000 H -0.0147050000 -4.3983810000 1.4450740000 (18b) 1panth_TS_cis_5 H 1.0579070000 -3.2312300000 2.2764900000 E = -1123.0279497 H -0.8262690000 -1.1337350000 2.5317840000 No. of Negative Frequencies = 1 174 H 3.9779910000 -3.1227320000 -0.8135620000 (18b-t) 1panth_TS_trans_5 E = -1123.025856 No. of Negative Frequencies = 1 (18c) 1panth_P_cis_5 freq = -495.8075 E = -1123.0627965 No. of Negative Frequencies = 0

C 1.5959500000 1.9040960000 1.8743730000 C 0.6403930000 0.8439620000 1.9886350000 C 3.17469 -1.80975 -0.33932 C 2.7870570000 1.7027510000 1.2040920000 C 2.58095 -0.48891 -0.33356 C 0.9775630000 -0.4375570000 1.4633120000 C 1.20551 -0.29489 -0.52420 C 2.2033650000 -0.6500360000 0.7947410000 C 2.77547 1.93783 0.17053 C 3.1346410000 0.4304280000 0.6591200000 C 1.45294 2.14902 -0.03792 C 4.3991640000 0.2106350000 -0.0323100000 C 0.61843 1.08031 -0.69457 C 4.6876180000 -1.0775400000 -0.5690040000 C 0.09343 -1.31212 -0.37923 C 3.7288240000 -2.1449260000 -0.4101650000 C -1.15923 -0.44434 -0.16823 C 2.5459060000 -1.9436210000 0.2369210000 C -0.83111 0.87290 -0.25268 H 3.4786580000 2.5325560000 1.1164950000 C -1.73521 2.01904 -0.01574 H 1.8566590000 -2.7708070000 0.3644050000 C -2.56618 2.03336 1.12293 C -0.2405680000 -1.3195730000 1.3186000000 C -3.45278 3.09490 1.34804 H -0.0518430000 -2.2578240000 0.7807650000 C -3.51634 4.16244 0.43915 C -2.0057640000 -2.3231650000 2.6616860000 C -2.67219 4.17077 -0.68401 H -2.0147080000 -3.1635400000 1.9483370000 C -1.78138 3.11203 -0.90407 H -2.1414970000 -2.7100600000 3.6721530000 H -0.01696 -1.97050 -1.26198 H -2.8259910000 -1.6358250000 2.4186250000 H -2.48593 1.22468 1.84539 O -0.7327550000 -1.6413860000 2.6493570000 H -2.71107 4.99879 -1.38437 C -1.2374480000 -0.4304960000 0.5270220000 H -1.13664 3.12016 -1.77934 C -0.9994900000 0.8774040000 0.6330260000 H -4.08340 3.09423 2.23141 C -1.5102900000 2.1575380000 0.2078540000 H -4.20454 4.98385 0.60912 C -2.7505040000 2.6449610000 0.6874820000 C 4.84283 0.47929 0.01791 C -0.7475670000 2.9651560000 -0.6694460000 C 4.52472 -1.97065 -0.21036 C -3.2262620000 3.8948030000 0.2721170000 C 3.41689 0.64951 -0.09106 H -3.3268720000 2.0365750000 1.3792480000 H 3.37327 2.73370 0.60204 C -1.2319080000 4.2103240000 -1.0832950000 O 0.41686 -2.16226 0.76221 H 0.2138210000 2.5984310000 -1.0173550000 C -0.46239 -3.28894 0.95951 C -2.4732670000 4.6794970000 -0.6176770000 H 0.03706 -3.95080 1.66852 H -4.1817980000 4.2565550000 0.6382660000 H -1.42802 -2.98113 1.38539 H -0.6447940000 4.8168220000 -1.7652330000 H -0.64011 -3.82572 0.01608 H -2.8454970000 5.6463660000 -0.9398690000 H 4.96707 -2.96311 -0.22921 Sn -2.7292220000 -1.1920670000 -0.8038210000 Sn -3.17462 -1.15063 -0.11308 C -1.9811930000 -3.0523650000 -1.5331470000 C -3.88132 -1.36426 1.89055 H -2.6493840000 -3.4662630000 -2.2967230000 H -3.04692 -1.37091 2.60124 H -0.9899270000 -2.9191270000 -1.9815480000 H -4.54350 -0.52840 2.14520 H -1.8955990000 -3.7872870000 -0.7237560000 H -4.44496 -2.29630 2.01054 C -4.5853620000 -1.5122770000 0.1991730000 C -3.24173 -3.04506 -1.10014 H -5.3974370000 -1.6018600000 -0.5314140000 H -2.45169 -3.13634 -1.85489 H -4.5604090000 -2.4302190000 0.7969070000 H -3.13332 -3.86915 -0.38646 H -4.8162670000 -0.6717660000 0.8638040000 H -4.20648 -3.15918 -1.60822 C -2.9750550000 0.2274690000 -2.3647860000 C -4.38790 0.22195 -1.19773 H -3.6678880000 -0.1425130000 -3.1291310000 H -4.74370 1.02871 -0.54797 H -3.3658430000 1.1706930000 -1.9661700000 H -3.80996 0.67740 -2.01026 H -2.0111630000 0.4382800000 -2.8412170000 H -5.25577 -0.28784 -1.63215 H -0.1240220000 0.9029150000 2.7597720000 H 0.98403 3.09914 0.20562 H 1.3728700000 2.8720920000 2.3112030000 H 0.58484 1.33049 -1.77805 C 5.9110770000 -1.3081750000 -1.2485130000 C 5.40069 -0.83741 -0.04786 C 5.3727270000 1.2340190000 -0.2035440000 C 6.80374 -1.01620 0.05820 H 5.1942330000 2.2268400000 0.1925580000 C 5.74020 1.57741 0.17950 C 6.8426700000 -0.2917380000 -1.4036210000 C 7.65214 0.06957 0.22209 H 7.7764990000 -0.4742460000 -1.9245690000 H 7.20514 -2.02481 0.00794 C 6.5653650000 0.9917430000 -0.8725550000 C 7.10886 1.37922 0.27938 H 7.2907900000 1.7903460000 -0.9888310000 H 5.35405 2.59018 0.20448 H 6.1067170000 -2.2998590000 -1.6475290000 H 8.72422 -0.07669 0.30166

175 H 7.77159 2.23052 0.39630 H 7.0229440000 -2.0057020000 -0.7604570000 H 2.51523 -2.66360 -0.44414 C 6.9972790000 1.4004490000 -0.5103780000 H 5.2907610000 2.6126450000 -0.1046710000 H 8.5644550000 -0.0587170000 -0.8907040000 (18c-t) 1panth_P_trans_5 H 7.6701330000 2.2504240000 -0.5576310000 E = -1123.068554 H 2.3905850000 -2.6498410000 0.0254560000 No. of Negative Frequencies = 0

(19a) ene_SM_up E = -1124.2245658 No. of Negative Frequencies = 0

C 3.0444600000 -1.7850220000 -0.0301930000 C 2.4817490000 -0.4699480000 0.2060670000 C 1.1273990000 -0.2964280000 0.5252270000 C 2.7086980000 1.9995490000 0.0801190000 C 1.4009670000 2.1920300000 0.3826810000 C 0.5338060000 1.0518270000 0.8408880000 C -0.0102670000 -1.2744560000 0.3448860000 C -1.1829980000 -0.3721110000 -0.0481720000 C -0.8788810000 0.9188350000 0.2416010000 C -2.3887170000 -4.3802330000 -1.4537460000 C -1.7764010000 2.0864060000 0.1389140000 C -2.7090220000 -3.0629060000 -1.0951140000 C -1.7804750000 3.0744510000 1.1452300000 C -1.8090480000 -2.2640360000 -0.3750850000 C -2.6647460000 4.1584010000 1.0787140000 C -0.5472170000 -2.7907020000 0.0000780000 C -3.5508290000 4.2814070000 -0.0039610000 C -0.2458510000 -4.1230400000 -0.3478270000 C -3.5363520000 3.3177060000 -1.0244150000 C -1.1487810000 -4.9114720000 -1.0724090000 C -2.6513690000 2.2330320000 -0.9560550000 H -3.0970640000 -4.9826320000 -2.0124590000 H 0.2114910000 -2.0696980000 -0.3837180000 H -3.6707230000 -2.6453600000 -1.3835350000 H -1.1078310000 2.9793290000 1.9935480000 H 0.6979770000 -4.5507490000 -0.0236650000 H -4.2034770000 3.4161120000 -1.8750030000 H -0.8910910000 -5.9343380000 -1.3270690000 H -2.6089830000 1.5104740000 -1.7658710000 C -2.2156660000 -0.8410330000 -0.0426480000 H -2.6661990000 4.9032370000 1.8680890000 H -3.2257220000 -0.6675670000 -0.4512090000 H -4.2349030000 5.1220190000 -0.0561790000 C -1.2922490000 0.2540720000 -0.5607890000 C 4.7369120000 0.5053630000 -0.1872900000 C -0.4553150000 0.1518240000 -1.5647200000 C 4.3731150000 -1.9450810000 -0.3036540000 C 0.6005240000 0.5806910000 -2.3922770000 C 3.3299060000 0.6781510000 0.0676920000 C 1.9457740000 0.5129280000 -1.9171280000 H 3.3057990000 2.8560570000 -0.2134660000 C 0.3697940000 1.0673190000 -3.7122760000 O -0.4401130000 -1.9106270000 1.6011980000 C 3.0024920000 0.9292530000 -2.7280650000 C 0.5097760000 -2.8663010000 2.1285020000 H 2.1301900000 0.1422240000 -0.9126380000 H 0.0704890000 -3.2690770000 3.0417950000 C 1.4383380000 1.4792050000 -4.5098160000 H 0.6804200000 -3.6844570000 1.4127340000 H -0.6486950000 1.1155470000 -4.0842250000 H 1.4674560000 -2.3827380000 2.3622060000 C 2.7603140000 1.4138850000 -4.0278670000 H 4.7884670000 -2.9356060000 -0.4693040000 H 4.0176250000 0.8828440000 -2.3457750000 Sn -3.0791230000 -1.2863650000 -0.3749440000 H 1.2473400000 1.8548350000 -5.5101010000 C -4.3745420000 -0.6367940000 1.1802890000 H 3.5856020000 1.7363390000 -4.6539170000 H -3.9546260000 -0.9199950000 2.1512110000 O -2.2806860000 -0.5964230000 1.4020440000 H -4.4730110000 0.4549440000 1.1512640000 C -3.2604270000 -1.4032290000 2.0984160000 H -5.3720310000 -1.0794270000 1.0835460000 H -3.2735870000 -1.0527150000 3.1310250000 C -2.7188310000 -3.3832700000 -0.3283430000 H -4.2556120000 -1.2726720000 1.6503740000 H -2.1346040000 -3.6949990000 -1.2025230000 H -2.9872900000 -2.4643270000 2.0689310000 H -2.1557230000 -3.6292020000 0.5778620000 C 0.4341260000 -1.9727590000 0.7461280000 H -3.6577040000 -3.9482030000 -0.3280660000 C 1.7729900000 -2.1253500000 0.6340290000 C -3.9333250000 -0.8059600000 -2.2744060000 Sn -1.3969020000 2.0798630000 0.5891780000 H -4.5408430000 0.1040110000 -2.2093370000 C -0.5151140000 3.5575790000 -0.6679980000 H -3.1564360000 -0.6542680000 -3.0328790000 H 0.5149270000 3.2790680000 -0.9211240000 H -4.5793250000 -1.6258250000 -2.6098060000 H -1.0757100000 3.6501430000 -1.6055280000 H 0.9607320000 3.1850750000 0.3367900000 H -0.4965920000 4.5377120000 -0.1771920000 H 0.4003720000 1.1504130000 1.9383580000 C -3.4435470000 2.5370280000 0.9672970000 C 5.2629940000 -0.8133740000 -0.3695420000 H -4.0063880000 2.6070530000 0.0297340000 C 6.6460430000 -0.9957570000 -0.6235850000 H -3.8834020000 1.7457990000 1.5840280000 C 5.6480920000 1.6016420000 -0.2618460000 H -3.5433290000 3.4907630000 1.4979570000 C 7.5075960000 0.0896340000 -0.6965760000 C -0.2789800000 1.9091380000 2.3902710000

176 H -0.3496980000 2.8263950000 2.9865090000 C -2.3155230000 1.8023330000 -0.2132650000 H -0.6711850000 1.0710010000 2.9761170000 Sn 2.4659420000 -1.7521760000 0.0255810000 H 0.7776430000 1.7233290000 2.1653660000 C 2.2425700000 -2.6959810000 -1.8661620000 H 0.0238110000 -1.1882870000 1.3795870000 H 1.1793330000 -2.8794510000 -2.0608440000 C 2.7859590000 -1.3295910000 1.3521700000 H 2.6325340000 -2.0592160000 -2.6673700000 C 2.4826880000 -0.5893320000 2.5150300000 H 2.7700640000 -3.6558960000 -1.8960350000 C 4.1065900000 -1.2913800000 0.8570980000 C 4.4771050000 -1.1416250000 0.3902770000 C 3.4649040000 0.1828200000 3.1462730000 H 4.8257380000 -0.4521110000 -0.3870510000 H 1.4818270000 -0.6309660000 2.9341140000 H 4.5520300000 -0.6383740000 1.3614230000 C 5.0920640000 -0.5219540000 1.4898280000 H 5.1487040000 -2.0074740000 0.4031880000 H 4.3539260000 -1.8625520000 -0.0346510000 C 1.7721470000 -3.0321250000 1.5781410000 C 4.7738080000 0.2226020000 2.6362210000 H 2.4953330000 -3.8268930000 1.7930720000 H 3.2131950000 0.7475020000 4.0384630000 H 1.6060790000 -2.4523180000 2.4924770000 H 6.1017330000 -0.5030180000 1.0922750000 H 0.8245570000 -3.4969580000 1.2836010000 H 5.5342070000 0.8190960000 3.1294070000 H -1.3558630000 -1.8741390000 1.1724810000 H 2.1640810000 -2.8442060000 -0.0865050000 H -0.7852950000 1.5326100000 1.2544580000 C -3.3552550000 0.9916830000 0.4173610000 C -3.2784890000 0.5694470000 1.7673080000 (19b) ene_TS_up C -4.4730100000 0.5823410000 -0.3454050000 E = -1124.209813 C -4.2686240000 -0.2491190000 2.3184720000 No. of Negative Frequencies = 1 H -2.4457140000 0.8892010000 2.3863720000 freq = -401.2326 C -5.4610700000 -0.2415590000 0.2048170000 H -4.5431080000 0.8935780000 -1.3848480000 C -5.3628110000 -0.6666290000 1.5397180000 H -4.1933760000 -0.5600810000 3.3559720000 H -6.3027060000 -0.5552160000 -0.4048720000 H -6.1294940000 -1.3029950000 1.9698310000 H -2.5516230000 2.2082130000 -1.1968950000

(19c) ene_P_up E = -1124.263408 No. of Negative Frequencies = 0

C 1.9253090000 4.5552610000 -1.4469260000 C 2.3152180000 3.4287540000 -0.7079850000 C 1.3639770000 2.5650210000 -0.1464050000 C -0.0167520000 2.8279450000 -0.3226060000 C -0.3980230000 3.9667370000 -1.0597100000 C 0.5593500000 4.8215490000 -1.6222530000 H 2.6728980000 5.2163920000 -1.8724810000 H 3.3722860000 3.2147220000 -0.5677290000 H -1.4536910000 4.1960520000 -1.1669440000 H 0.2421360000 5.6954090000 -2.1822130000 C -1.4327130000 4.5046680000 -1.4817660000 C 1.8395370000 1.3309500000 0.5971270000 C -0.2571150000 3.9321120000 -0.9760950000 H 2.9402390000 1.3074240000 0.5420490000 C -0.2554360000 2.6167020000 -0.4887430000 C 1.2669950000 0.0292550000 0.0358900000 C -1.4337520000 1.8482800000 -0.5256340000 C -0.0038010000 -0.0745030000 -0.3096260000 C -2.6105790000 2.4248510000 -1.0307300000 C -1.0173430000 -0.9804990000 -0.7691940000 C -2.6127050000 3.7467230000 -1.5019310000 C -1.6694100000 -1.8581720000 0.1323460000 H -1.4289280000 5.5230430000 -1.8561710000 C -1.4652350000 -0.9228140000 -2.1118440000 H 0.6657550000 4.5077060000 -0.9576250000 C -2.7222130000 -2.6687250000 -0.3046610000 H -3.5236910000 1.8391220000 -1.0699420000 C -2.5136550000 -1.7427980000 -2.5435150000 H -3.5294380000 4.1775430000 -1.8913620000 H -0.9800910000 -0.2346550000 -2.7978300000 C 0.9966610000 2.0132350000 0.1017930000 C -3.1482470000 -2.6166090000 -1.6432230000 H 1.8749670000 2.5669540000 -0.2703420000 H -3.2203500000 -3.3270630000 0.3996740000 C 1.1285370000 0.5240940000 -0.1611270000 H -2.8415060000 -1.6978190000 -3.5772850000 C -0.0014820000 -0.2202020000 -0.2028510000 H -3.9699700000 -3.2416330000 -1.9775050000 C 0.0618410000 -1.7062150000 -0.3173810000 O 1.4721780000 1.3445550000 2.0150550000 C -0.5950170000 -2.5291460000 0.6199400000 C 2.0495030000 2.4564180000 2.7449050000 C 0.8057370000 -2.3108100000 -1.3479730000 H 1.8034100000 2.2963920000 3.7950120000 C -0.4735610000 -3.9223970000 0.5515770000 H 3.1419480000 2.4776900000 2.6209410000 C 0.9249550000 -3.7076130000 -1.4210960000 H 1.6328420000 3.4124370000 2.4056030000 H 1.2734190000 -1.6819620000 -2.1009270000 C -1.0325570000 1.9258850000 0.2704590000 C 0.2927240000 -4.5173890000 -0.4661080000 H -0.9716190000 -4.5431910000 1.2891360000 177 H 1.5022570000 -4.1585230000 -2.2222510000 C 3.0134190000 -1.8525280000 1.5395590000 H 0.3857610000 -5.5972830000 -0.5175970000 H 4.0178930000 -2.1279830000 1.8806940000 O 1.0019630000 2.1220460000 1.5709750000 H 2.4225060000 -1.5395030000 2.4072830000 C 1.0828360000 3.4841870000 2.0567700000 H 2.5369340000 -2.7373330000 1.1004770000 H 1.2124730000 3.4179470000 3.1376740000 H -1.1841760000 -2.0753500000 1.4125750000 H 1.9453400000 4.0047500000 1.6138260000 H -1.5531660000 0.4491270000 1.0734610000 H 0.1688130000 4.0448680000 1.8273150000 C -3.7676830000 -0.6710380000 -0.0601590000 C -1.3986000000 0.4032200000 -0.0175040000 C -4.2047180000 -0.0098680000 1.1268560000 C -2.4792060000 -0.4473950000 -0.6350570000 C -4.6740460000 -1.5819560000 -0.6809610000 Sn 3.0944440000 -0.2770650000 0.1141300000 C -5.4707320000 -0.2604350000 1.6608410000 C 3.9901590000 -0.9691470000 -1.6985390000 H -3.5540490000 0.7110240000 1.6134940000 H 3.7845970000 -2.0359940000 -1.8426540000 C -5.9356410000 -1.8262290000 -0.1405440000 H 3.6018900000 -0.4197350000 -2.5640340000 H -4.3587460000 -2.0953030000 -1.5856360000 H 5.0767870000 -0.8286720000 -1.6635440000 C -6.3450000000 -1.1694170000 1.0368660000 C 4.2398980000 1.3737760000 0.8298990000 H -5.7845260000 0.2554190000 2.5628880000 H 4.4598950000 2.0833830000 0.0232080000 H -6.6054960000 -2.5270830000 -0.6285920000 H 3.6779270000 1.8928170000 1.6146550000 H -7.3270330000 -1.3600400000 1.4565780000 H 5.1931940000 1.0334510000 1.2503290000 H -2.2501500000 -0.9226710000 -1.5866280000

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188 BIOGRAPHICAL SKETCH

Education

2018 Ph.D. in Chemistry, Florida State University, Tallahassee, FL 2015 M.S. in Chemistry, Florida State University, Tallahassee, FL 2012 B.S. in Chemistry, Rhodes College, Memphis, TN

Publications

7. Hughes, A. M.; dos Passos Gomes, G.; Alabugin, I. V. Stereoelectronic Influence of a “Spectator” Propargylic Substituent Can Override Aromaticity Effects in Radical Peri- cyclizations on Route to Expanded Polyaromatics. Submitted for publication.

6. Tsvetkov, N. P.; Gonzalez-Rodriguez, E.; Hughes, A. M.; dos Passos Gomes, G.; White, F. D.; Kuriakose, F.; Alabugin, I. V. Radical Alkyne peri-Annulation Reactions for the Synthesis of Functionalized Phenalenes, Benzanthrenes, and Olympicene. Angew. Chem. 2018, 130, 3713-3717. (DOI: 10.1002/ange.201712783)

5. Sedenkova, K. N.; Averina, E. B.; Grishin, Y. K.; Kolodyazhnaya, J. V.; Rybakov, V. B.; Kuznetsova, T. S.; Hughes, A. M.; dos Passos Gomes, G.; Alabugin, I. V.; Zefirova, N. S. Substituent effects on stereoselectivity of dihalocarbene reactions with cyclohexadiene and on the reactivity of bis-dihalocyclopropanes in electrophilic nitrations en route to pyrimidine N-oxides. Org. Biomol. Chem. 2017, 15, 9433-9441. (DOI: 10.1039/C7OB02463K)

4. Syroeshkin, M. A.; Krylov, I. B.; Hughes, A. M.; Alabugin, I. V.; Nasybullina, D. V.; Sharipov, M. Yu.; Gultyai, V. P.; Terent'ev, A. O. Electrochemical behavior of N‐ oxyphthalimides: Cascades initiating self‐sustaining catalytic reductive N―O bond cleavage. J. Phys. Org. Chem. 2017, 30, e3744. (DOI: 10.1002/poc.3744)

3. Vasilevsky, S. F.; Davydova, M. P.; Mamatyuk, V. I.; Tsvetkov, N.; Hughes, A. M.; Baranov, D. S.; Alabugin, I. V. Full Cleavage of C≡C Bond in Electron-Deficient Alkynes via Reaction with Ethylenediamine. Aust. J. Chem. 2017, 70, 421-429. (DOI: 10.1071/CH17026)

2. Pati, K.; dos Passos Gomes, G.; Harris, T.; Hughes, A. M.; Phan, H.; Banerjee, T.; Hanson, K.; Alabugin, I. V. Traceless Directing Groups in Radical Cascades: From Oligoalkynes to Fused Helicenes without Tethered Initiators. J. Am. Chem. Soc. 2015, 137 (3), 1165- 1180. (DOI: 10.1021/ja510563d)

1. Pati, K.; Hughes, A. M.; Phan, H.; Alabugin, I. V. Exo-Dig Radical Cascades of Skipped Enediynes: Building a Naphthalene Moiety within a Polycyclic Framework. Chem. Eur. J. 2014, 20, 390-393. (DOI: 10.1002/chem.201304092)

189