Development of Constrained Geometry Complexes of Group 4

Home , Polyolefin

A Dissertation

entitled

Development of Constrained Geometry Complexes of

Group 4 and 5 Metals

Ryan Thomas Rondo

Submitted to the Graduate Faculty as a partial fulfillment of the requirements for

the Doctor of Philosophy Degree in Chemistry

Dr. Mark R. Mason, Committee Chair

Dr. Patricia Komuniecki, Dean College of Graduate Studies

The University of Toledo

May 2010

An abstract of

Development of Constrained Geometry Complexes of

Group 4 and 5 Metals

Ryan Thomas Rondo

Submitted to the Graduate Faculty in partial fulfillment of the requirements for

the Doctor of Philosophy Degree in Chemistry

The University of Toledo

May 2010

Constrained geometry catalysts (CGC) are known to be active in the polymerization and copolymerization of alkenes with a distinct control over polymer tacticity. The tethering of one 5-cyclopentadienyl moiety and one pendant donor gives these compounds an accessible metal center as well as ability to maintain their structure throughout the catalytic process. Complexes of this type typically feature one pendant amido donor. Replacement of the pendant amido donor with a nitrogen heterocycle such as an indolyl- or pyrrolyl-group should result in electrophilic metal centers due to reduced N M donation, a consequence of electron delocalization of the nitrogen lone pair in the aromatic system. This dissertation reports the development of a new series of constrained geometry ligands that feature indolyl- and pyrrolyl- donor moieties.

iii

In chapter 2, the synthesis and characterization of a series of acetal precursors and their corresponding di(3-methylindolyl)ethane and dipyrrolylethane constrained geometry ligands is reported. Within this report are two new acetal precursors, fluorenyl acetaldehyde diethylacetal, and indenyl acetaldehyde diethylacetal. Also described are the new constrained geometry ligands fluorenyl di(3-methylindolyl)ethane (H3FDI), fluorenyl dipyrrolylethane (H3FDP), indenyl di(3-methylindolyl)ethane (H3IDI), and

1 indenyl dipyrrolylethane (H3IDP). These compounds have been characterized by H and

13C NMR spectroscopy as well as mass spectrometry and elemental analysis. The molecular structure of H3FDI·THF has been confirmed by X-ray crystallography. This new set of ligands serves as a framework for constrained geometry complexes of group 4 and 5 transition metals.

Chapter 3 reports the synthesis and characterization of group 4 and 5 constrained geometry complexes of fluorenyl di(3-methylindolyl)ethane (H3FDI) and indenyl di(3- methylindolyl)ethane (H3IDI). Within this report are the first examples of 3- methylindolyl-based CGC‟s of group 4 and 5 metals, specifically in the complexes

(HFDI)Zr(NEt2)2(THF), (HFDI)Ti(NEt2)2, (IDI)Zr(NEt2), which were prepared using

t amine elimination methods, and (IDI)Nb(N Bu)(py), (IDI)Nb(NPh), (FDI)Zr(CH3), and

(FDI)Ti(CH3), which were prepared via salt metathesis. These complexes have been characterized by 1H and 13C NMR spectroscopy. X-ray crystallography confirmed the

5 bidentate nature of the HFDI ligand in (HFDI)Zr(NEt2)2(THF) as well as the - coordination of the indene moiety in (IDI)Zr(NEt2). The structures of analogous

t 1 13 complexes (HFDI)Ti(NEt2)2 and (IDI)Nb(N Bu)(py) were determined by H and C

5 NMR spectroscopy. Another -coordinated complex, (FDI)Zr(CH3) was characterized

iv by NMR spectroscopy. This complex exhibits a methyl resonance indicative of transition metal-methyl complexes. These constrained geometry complexes serve as a representative sample for the preparation of various CGC‟s with this ligand framework.

Chapter 3 also reports the initial preparation of titanium metal-imido complexes that feature di(3-methylindolyl)methane ligands with one neutral pendant donor. Three complexes, (tBuN)Ti{(2-py)di(3-methylindolyl)methane}, (tBuN)Ti{(N-

t methylimidazolyl)di(3-methylindolyl)methane}, and ( BuN)Ti{(2-MeOC6H4)di(3- methylindolyl)methane} were characterized by 1H and 13C NMR spectroscopy. X-ray crystallographic analysis of (tBuN)Ti{(2-py)di(3-methylindolyl)methane}, while incomplete, confirmed the connectivity of this complex.

In chapter 4, the in situ generation of copper(I)-pyridine derivative complexes and their olefin binding properties are reported. The new complexes [(Me- nic)3Cu(NCCH3)]PF6 (Me-nic = methylnicotinate), [(3-MeOpy)3Cu(NCCH3)]PF6, and

1 13 [(3-HOpy)3Cu(NCCH3)]PF6 have been generated in situ and characterized by H and C

NMR spectroscopy. These complexes were examined for their affinity to bind ethylene, propylene, 1-hexene, and cis- and trans-3-hexene. Variable-temperature NMR spectra of these alkene complexes revealed a dynamic system with fast exchange between free and coordinated alkene at temperatures as low as 80 C. Using an extrapolation method, room temperature binding constants were determined for these alkene complexes. These copper(I) compounds exhibit binding constants for ethylene and propylene that are significantly lower than those of complexes featuring multidentate amine-based donor ligands. Furthermore, these complexes do not appear to bind 1-hexene, cis-3-hexene, or trans-3-hexene.

Appendix 1 reports the synthesis and characterization of metallophosphinate complexes of aluminum and gallium. These complexes are believed to consist of a

M2P2O4 (M = Al, Ga) ring structure, which was confirmed by X-ray crystallographic analysis of [Ph2AlO2PPh2]2. Specifically, the complexes [Ph2AlO2PPh2]2,

[Ph2GaO2PPh2]2, [Ph2AlO2P(OPh)2]2, and [Ph2GaO2P(OPh)2]2 have been synthesized.

Also reported in this appendix are reactions of triphenylaluminum and triphenylgallium with phosphonic acids. Products isolated in reactions with phosphonic acids were difficult to characterize due to their insoluble nature and amorphous morphology.

For my wife and my family whose patience and support guided me through these years. And especially for my father, who always encouraged me to succeed.

Acknowledgement

I would like to give thanks and express appreciation for my advisor, Dr. Mark R.

Mason. His continued guidance has proven invaluable to my development as a chemist.

Acknowledgement is needed for Dr. Bruce A. Averill for his guidance throughout the initial stages of my graduate career.

I would also like to thank Drs. Joseph Schmidt, Cora Lind, and Maria Coleman for serving on my committee. I would like to thank to Dr. Kristin Kirschbaum for her help in solving crystal structures. Thanks go to Mark R. Giolando and William Scharer who assisted Dr. Kirschbaum with work on the structure of 51·THF. Thanks go to Dr.

Yong-Wah Kim, for help with NMR spectroscopy. I am grateful to Steve Moder for his fabrication of glassware for my experiments. Thanks go to Pannee Burckel and Kristi

Mock for elemental analysis work. I would like to thank my group members Dr.

Nicholas Kingsley, Chris Yeisley, Adam Keith, Emmanuel Tive, Chris Gianopoulos,

Anirban Das, Michael Helmstadter, and Leonard Nyadong for their support. I am grateful for partial financial support provided by The University of Toledo

Interdisciplinary Research Initiation Award (Prof. Mark Mason, PI), which was used in the research reported in chapters 2 and 3. Finally I would like to thank my family and friends for their support. To my wife, Shannon, I appreciate your unwavering love and support through this time. I would not be the person I am today without you.

viii

Table of Contents

Abstract iii

Acknowledgements viii

Table of Contents ix

List of Appendix Contents xi

List of Figures xii

List of Tables xv

List of Abbreviations xvi

Chapter 1 Group IV and V Transition Metal Complexes: A Concise Review of

Constrained Geometry Catalysts and Transition Metal Imido

Complexes

1.1 Introduction 1

1.2 Ziegler-Natta and Phillips-Type Catalysts 2

1.3 Single-Site Catalysts 5

1.4 Catalyst Activation 7

1.5 Constrained Geometry Catalysts 9

1.6 Recent Constrained Geometry Catalysts 12

1.7 Transition Metal-Imido Complexes 15

1.8 Research Statement 19

Chapter 2 Trianionic Indole- and Pyrrole-Based Constrained Geometry Ligands

2.1 Introduction 23

2.2 Experimental 28

2.3 X-ray Crystallography 37

2.4 Results and Discussion 38

2.4.1 Synthesis of Diethylacetals 39

2.4.2 Synthesis of Constrained Geometry Ligands 43

2.5 Conclusions 54

Chapter 3 Constrained Geometry and Related Complexes of Group 4 and 5 Metals

3.1 Introduction 55

3.2 Experimental 61

3.3 X-ray Crystallography 71

3.4 Results and Discussion 74

3.4.1 Preparation and Characterization of (HFDI)M(NEt2)2 75

3.4.2 Preparation and Characterization of (IDI)Zr(NEt2) 82

3.4.3 Preparation and Characterization of (FDI)M(CH3) 87

3.4.4 Preparation and Characterization of 91

(IDI)Nb(=NR)(py)x; (x = 0, 1)

3.4.5 Titanium-Imido Complexes of 94

Di(3-methylindolyl)methanes

3.5 Conclusions 99

Chapter 4 Olefin Binding Studies of Copper(I) Pyridine Derivative Complexes

4.1 Introduction 101

4.2 Experimental 109

4.3 Results and Discussion 117

4.3.1 In-situ Generation of Copper-Olefin Complexes 117

4.3.2 Olefin Binding Studies 118

4.4 Conclusions 126

Chapter 5 Concluding Remarks 127

References 132

Appendix 1 Molecular Phosphinates and Phosphonates of Aluminum and Gallium

A.1 Introduction 145

A.2 Experimental 148

A.3 X-ray Crystallography 153

A.4 Results and Discussion 154

A.5 Conclusions 161

A.6 References 162

Appendix 2 CIF Files for Compounds

CIF File for H3FDI·THF 166

CIF File for (HFDI)Zr(NEt2)2(THF) 181

CIF File for (IDI)Zr(NEt2) 202

List of Figures

Figure 1.1 Zielger-Natta polymerization mechanism for the formation of 4

isotactic polypropylene.

Figure 1.2 Different tacticity forms of polypropylene. 5

Figure 1.3 Typical constrained geometry catalysts. 10

Figure 2.1 Typical constrained geometry ligand structure. 24

Figure 2.2 Numbering schemes for indole, fluorene, and 28

indene, respectively.

Figure 2.3 1H NMR spectrum of fluorenyl acetaldehyde diethylacetal (48). 41

Figure 2.4 1H NMR spectrum of the aliphatic region of 49. 42

Figure 2.5 gCOSY spectrum of the aromatic region of 51 in chloroform-d. 45

Figure 2.6 ORTEP diagram of 51. Thermal ellipsoids are drawn at the 30% 46

probability level. Non-nitrogen bound hydrogen atoms

are omitted for clarity.

1 Figure 2.7 H NMR spectrum of the aromatic region of H3FDP (52). 48

Figure 2.8 gHMBC spectrum of H3FDP (52). 49

Figure 2.9 NMR numbering scheme for H3IDI (53 ). 51

Figure 2.10 1H NMR spectrum of the aromatic region of 53. 51

Figure 2.11 1H NMR spectrum of the aliphatic region of 53. 51

Figure 2.12 gCOSY spectrum of the aromatic region of 53. 52

xii

Figure 3.1 1H NMR spectrum of 58. The top spectrum is of the 77

aromatic region of 58.

Figure 3.2 ORTEP diagram of 58. Thermal ellipsoids are drawn at the 30% 79

probability level. Hydrogen atoms are omitted for clarity.

Figure 3.3 1H NMR spectrum of the aromatic region of 60. 84

Figure 3.4 1H NMR spectrum of the aliphatic region of 60. 84

Figure 3.5 ORTEP diagram of 60. Thermal ellipsoids are drawn at 86

the 30% probability level. Hydrogen atoms are omitted

for clarity.

Figure 3.6 ORTEP diagram of the zirconium core of 60. 86

Thermal ellipsoids are drawn at the 30% probability level.

Hydrogen atoms, a toluene solvate molecule, and the indolyl

moieties are omitted for clarity.

Figure 3.7 1H NMR spectrum of 61. The top spectrum is of the 89

aromatic region.

Figure 3.8 1H NMR spectrum of the aliphatic region of 63. 93

Figure 3.9. Variable temperature 1H NMR stack-plot spectra of 66. 97

Figure 4.1 Dewar-Chatt-Duncanson model of bonding in transition 103

metal-olefin complexes.

Figure 4.2 Nickel(II) dithiolene system for el ectrochemical olefin separation 104

Figure 4.3 A linear plot of [C2H4] versus chemical shift in the presence of 115

complex 77. Extrapolation to a [C2H4] of “zero” allows for the

shift determination of 4.865 ppm for bound C 2H4. Data obtained

xiii

in acetone-d6.

Figure A.1 Some typical secondary building units (SBU). Bridging 2-oxo 146

atoms along each edge are omitted for clarity.

31 Figure A.2 P NMR spectrum of [Ph2AlO2PPh2]2. 156

Figure A.4 31P NMR spectrum of D. 159

xiv

List of Tables

Table 2.1 Crystal data and structure refinement details for 38

compound 51·THF

Table 2.2 Selected bond distances and angles for compound 51·THF 46

Table 3.1 Crystal data and structure refinement details for 58 and 60 73

Table 3.2 Selected bond distances and angles for complex 58 79

Table 3.3 Selected bond distances and angles for complex 60 87

Table 4.1 Summary of equilibrium constants (K) at 20 °C 123

Table 4.2 Summary of olefinic proton chemical shift changes 124

at 20 °C (ppm)

Table 4.3 Summary of variable temperature equilibrium constants 124

for ethylene binding

List of Abbreviations

2D two dimensional acac acetylacetonate CCD charge coupled device CDCl3 chloroform-d C6D6 benzene-d6 CGC constrained geometry catalyst CIF crystallographic information file g-COSY gated correlation spectroscopy Cp cyclopentadienyl CpA cyclopentadienyl acetaldehyde diethylacetal DBU diazabicycloundecene dien diethylenetriamine ES electrospray FA fluorenyl acetaldehyde diethylacetal H3FDI fluorenyl di(3-methylindolyl)ethane H3FDP fluorenyl di(2-pyrrolyl)ethane H3IDI indenyl di(3-methylindolyl)ethane H3IDP indenyl di(2-pyrrolyl)ethane g-HMBC gated-heteronuclear multiple bond coherence g-HMQC gated-heteronuclear multiple quantum coherence HRMS high-resolution mass spectrometry IA indenyl acetaldehyde diethylacetal IR infrared MAO methylaluminoxanes Me4Cp tetramethylcyclopentadienyl Me5-dien pentamethyldiethylenetriamine Me-nic methylnicotinate Mes 2,4,6-trimethylphenyl NMR nuclear magnetic resonance ORTEP Oak-Ridge Thermal Ellipsoid Plot PDI polydispersity index phen 1,10-phenanthroline py pyridine Pz pyrazolyl SBU secondary building unit SSC single-site catalyst THF tetrahydrofuran

xvi

TMI transition metal-imido VT variable-temperature

xvii

Chapter One

Group IV and V Transition Metal Complexes: A Concise Review of

Constrained Geometry Catalysts and Transition Metal Imido

Complexes

1.1 Introduction

Constrained geometry catalysts, abbreviated as CGC, are the culmination of decades of research and development of catalyst systems for the oligomerization and polymerization of alkenes such as ethylene and propylene.1 The name constrained geometry catalyst was coined by Stevens et al., and originates from complexes that feature a -bonded moiety (e.g. cyclopentadienyl, indenyl, fluorenyl) bridged to a second donor group on the same metal center.2 This bridge creates a relativevly small angle between the centroid of the -system and the additional donor, giving the metal complex a „constrained‟ geometry. Stevens et al. believed the reduced angle would provide an active catalyst for polymerization of alkenes. This hypothesis was supported by comparison of these CGC‟s to the performance of typical polymerization catalysts such as Ziegler-Natta systems, metallocenes, and other single-site catalysts, revealing a higher activity in ethylene polymerization.

The first constrained geometry catalysts were synthesized in the early 1990‟s and the first structure published in the open literature was scandium complex 1 by Shapiro 1 and Bercaw,3 followed shortly thereafter by the structure of titanium complex 2 by

Okuda.4 Several researchers in academia and industry have since prepared constrained geometry catalysts consisting of group 4 transition metals.1,5 These catalysts have been extensively studied for their activity towards polymerizing ethylene and propylene as well as for their ability to incorporate larger -olefins (i.e. 1-hexene) into polyethylene chains during copolymerizations.

H Si Sc Sc Si Si Ti Cl H Cl N PMe3 PMe3 N N tBu tBu tBu 1 2

In order to fully understand the progression towards the first constrained geometry catalysts as well as to identify opportunities for further development, one must consider early alkene oligomerization and polymerization catalysts, such as the Ziegler-

Natta system.

1.2 Ziegler-Natta and Phillips-Type Catalysts

In 1953, Karl Ziegler produced suspensions of finely divided, heterogeneous

6 TiCl3 by reduction of TiCl4 with AlEt3 in hydrocarbon solutions. Interestingly, Ziegler found that finely divided mixture polymerized ethylene under moderate conditions.7,8

This development led to further interest in generating transition metal alkyl complexes for polymerization. These titanium systems were further pursued by Natta, who found that these transition metal alkyl systems will polymerize propylene to mostly one

9,10 stereoisomer: isotactic polypropylene. These TiCl4-AlEt3 systems are known as

Ziegler-Natta catalysts, and the stereoregular polypropylene they produce earned Ziegler and Natta the Nobel Prize in 1963.

Around the same time Ziegler-Natta systems were being developed, some chromium catalysts were also discovered to polymerize ethylene into highly linear polymer chains with a well defined polydispersity. Two systems are typically listed in the initial development of chromium alkene polymerization catalysts, both of which are

11 composed of chromium on silica; Phillips developed Cr2O3 and Union Carbide

12 developed Cp2Cr. Though these catalysts are known to polymerize ethylene, the active sites of the catalysts are not well understood. Some research suggests that the active site contains Cr3+ metal centers, while other data suggests that Cr2+ is the active catalytic component.13

Although Ziegler-Natta and Phillips-type catalysts are used frequently in industry for the polymerization of alkenes, these systems are not free of drawbacks. Due to the heterogeneous nature of the Ziegler-Natta and Phillips systems, the exact mechanism of the polymerization could not be studied directly. This lack of characterization led to many questions about polymer growth. Interest in the polymerization mechanism of these systems provoked the development of homogeneous catalysts such as metallocenes

(described in Section 1.3) that could be used as models to study the polymerization mechanism.

The ethylene polymerization mechanism of these transition metal alkyl complexes is explained by the Cossee-Arlman mechanism:14-16

R R R CH2R CH CH 2 2 H2C CH2 CH CH2 C2H4 2 C2H4 etc. Ti Ti Ti CH2 Ti C CH2 H2

The metal alkyl complex must have a vacant site for alkene coordination. Upon coordination, the alkene can insert into the metal-alkyl bond through a four-membered transition state. After insertion, a vacant site is once again open for alkene coordination, and chain propagation can occur.

The mechanism for polymerization of propylene and other -olefins is not as simple since more than one stereoisomer can be produced in the process. This depends on the orientation and insertion of the coordinating alkene to the alkyl group on the transition metal. In this process isotactic, syndiotactic or atactic polypropylene is produced. Furthermore, regioselectivity can be affected by the catalyst, wherein 1,2- or

2,1-insertion can occur, thereby changing the resulting polymer. Control over polypropylene tacticity in Ziegler-Natta catalytic systems and metallocenes has been explained by Bochmann et al. who details the stereoselectivity of these types of catalysts.17 As shown in Figure 1.1, isotactic polypropylene is produced from steric interaction of the polymer chain to a neighboring chloride (Cl*). This interaction hinders rotation of the polymer chain, and a single orientation is favored in the polymerization process, thus resulting in isotactic polypropylene.

P P Ti Cl* H Ti Cl* H H CH3 H CH3 H H Cl Ti Cl Cl Ti CH3 H3C TiCl Cl TiCl Cl

Cl Cl Favored orientation Disfavored orientation

Figure 1.1. Zielger-Natta polymerization mechanism for the formation of isotactic

polypropylene

isotactic

syndiotactic

atactic

Figure 1.2. Different tacticity forms of polypropylene

1.3 Single-Site Catalysts

The confusion over the mechanism of Ziegler-Natta and chromium systems in polymerizing alkenes led to the discovery of single site catalysts (SSC). The major advantage of single-site catalysts is their homogeneous nature, meaning that every catalytic site is the same. Homogeneous catalysts finally made polymerization mechanistic studies possible. Another advantage to SSCs is that they tend to produce polymers with a well defined poly-dispersity index (PDI). Single-site catalysts have allowed for fine-tuning of metal complexes for targeting the production of a particular polymer. Until recently, SSC-produced polymers were not utilized on an industrial scale.

However, with recent advancements in technology and synthesis, SSC-polymers have made their way into the industrial sector; some analysts suggest that the SSC-polymer industry will grow at a rapid rate.18

Early single-site catalysts focused on bent metallocenes, namely titanocenes and zirconocenes, and to a lesser extent hafnocenes.19 These types of complexes have been of interest due to their high activity for polymerizing alkenes and for their versatility in

5 meeting a variety of polymerization conditions such as attaching them to silica as a support.19 Currently, the activities of many constrained geometry catalysts are compared to the activity of Cp2ZrMe2 activated with MAO. The high polymerization activity of these complexes arises from a stable intermediate formed during alkyl transfer to the coordinated ethylene, which happens via an -agostic interaction with the metal center.19

H 2 H2 H2 C C C CH Cp Cp CH Cp 2 Zr+ CH2 Zr+ 2 Zr+ Cp CH2 Cp CH2 Cp CH2 H H H

Research of metallocene catalysts has expanded into complexes with C2 and Cs symmetry. These compounds are termed ansa-metallocenes for the ansa bridge tethering two 5-cyclopentadienyl moieties. In these compounds, the catalyst activity, stereoselectivity, and molecular weight of the resulting polyolefin vary with the ligand used. The ligands in these catalysts typically feature cyclopentadienyl-, indenyl-, or

20 fluorenyl-type moieties. Complexes with C2 symmetry such as 3 and 4 are selective for

21 isotactic polypropylene, while complexes with Cs symmetry (5) typically produce syndiotactic polypropylene.

Cl Cl Cl Zr Cl Me2Si Ti Me2Si Zr Cl Cl

3 4 5

Metallocenes and ansa-metallocenes are not the only polymerization catalysts with attention for their catalytic activity. Recently, some highly active mid to late transition metal complexes featuring -diimine based ligands have been developed.22

Specifically, diimine complexes of nickel23 and palladium24 (6) have shown good activity for polymerizing ethylene, while the analogous complexes of cobalt exhibit poor activity.25 However, iron and cobalt catalysts with pyridine bis-imine ligands (7) have shown excellent activity towards ethylene polymerization.26 The disadvantage compared to some of the previous catalysts such as the nickel complexes is the tendency to undergo

-H elimination, which results in polymer chain termination. Steric hindrance supplied by the ligand helps counteract this; reinsertion after -H elimination in these catalysts provides more branching in the polymer chain.27 Therefore, a more sterically crowded set of ligands is desirable for transition metal alkene polymerization catalysts, reducing the probability of -H elimination.

N DIPP = Pri iPr DIPP NN DIPP Fe Ni N N Br Br DIPP Cl Cl DIPP 6 7

1.4 Catalyst Activation

It should be noted that all catalysts discussed to this point, including constrained geometry catalysts (described in section 1.5) must be activated with a proper reagent prior to the polymerization process. These activators have been described in detail elsewhere,28 but a brief summary will be provided here. The key to active metallocene polymerization catalysts is the generation of a cationic, 14 electron species via abstraction of an alkyl group (e.g. methyl) from the metal center. Depending on the catalyst used, typical activators such as methylaluminoxane (MAO), trialkylaluminum reagents, perfluoroarylboranes, or triphenylcarbenium (trityl) salts are employed.28

CH3 CH3 Zr + A Zr CH3 X

A = MAO, [Ph C][B(C F ) ], B(C F ) 3 6 5 4 6 5 3 X = [MAO-CH3], [B(C6F5)4], [(CH3)B(C6F5)3]

Ziegler-Natta catalysts utilize trialkylaluminum or monohalogenated dialkyl aluminum reagents for activation.7-10 Furthermore, Breslow and Newburg observed activation of Cp2TiCl2 with Et2AlCl, resulting in ethylene polymerization under mild conditions.29 Although these systems could be activated using alkylaluminum reagents, several titanium and zirconium metallocene systems were either inactive with these reagents or exhibited rapid deactivation to an inactive species during polymerization.30

In addition to the formation of inactive species, the activity of the active systems was fairly low, which ultimately limited their potential as industrial polymerization catalysts.

Interest in these complexes surged, however, when Sinn and Kaminsky reported reaction

31 of an inactive mixture of Cp2ZrCl2 and AlMe3 with water. Their reports outlined the discovery of a new activator, methylaluminoxane.30 Methylaluminoxane can be a useful activator for catalysts featuring chloro or amido moieties. The role of MAO in these reactions is two-fold: 1) generation of the methyl derivative of the complex, and 2) activation via methyl abstraction.

Highly Lewis-acidic perfluoroarylboranes such as tris(pentafluorophenyl)borane have been particularly useful in co-catalyst systems, specifically for allowing isolation and characterization of the catalytically active species and counterions.32,33 However, perfluoroarylboranes have typically resulted in catalysts with lower polymerization

8 activities. This is mainly due to considerable interaction of the counter ion, MeB(C6F5)3 with the metal center.

Triphenylcarbenium salts have also been employed as powerful alkide and hydride abstracting agents.32 These activators feature weakly-coordinating or non- coordinating anions which are beneficial to the polymerization process and typically result in more active catalysts than those of the perfluoroarylboranes.34 Each of these activators, whether it is an alkylaluminum reagent, MAO, FAB, or a trityl salt, must be carefully chosen to match the nature of the precatalyst. The combination of precatalyst and activator can have strong effects on the activity of the resulting catalyst for alkene polymerization.35

1.5 Constrained Geometry Catalysts

Attempts to improve control over polymer tacticity as well as improving copolymerizations of ethylene with -olefins have resulted in the synthesis and characterization of a class of compounds known as constrained geometry catalysts.

CGCs originated by exchanging one of the cyclopentadienyl donors of ansa-metallocenes with a pendant amido donor group. This vastly changes the electronics of the ligand, which remains dianionic in nature. The smaller bite angle of these ligands to a metal center is the origin of the term „constrained geometry‟. Generally, CGC ligands consist of three parts: i) an 5-cyclopentadienyl moiety, ii) an anionic or neutral pendant donor group (E), and iii) a bridge (Z) between the cyclopentadienyl moiety and pendant donor

(Figure 1.3). CGC‟s can be tailored to a variety of catalytic applications such as hydroboration36 or hydrogenation,37 but they are mostly being studied for their alkene

9 polymerization ability.5 One major advantage to CGC complexes is the modifications of the complex resulting in various effects on polymerization activity and -olefin incorporation rate.

Cp, Me4Cp, indene, fluorene, etc.

X M Z X Transition Metal SiR2 E CR2 X = Cl, NR2, etc. C R Z = 2 4 NAr C3R6 NR PR PAr BR E = PR O S "C"

Figure 1.3. Typical constrained geometry catalysts

Variations of any one of the aforementioned parts of the CGC ligand can have different effects on the activity and incorporation rates of these complexes. Figure 1.3 shows a short list of complexes that have already been synthesized. Several other derivatives of the cyclopentadienyl moiety have been explored and the use of non- symmetric cyclopentadienyl moieties results in chiral CGCs. It should be noted that increasing steric demand on the cyclopentadienyl moiety as well as the nature of the pendant donor can cause either 5: 1 or 1: 1 ligand coordination,5 and some late transition metal complexes adopt 3: 1 coordination.38 To date, the most common cyclopentadienyl fragments used are cyclopentadiene or tetramethylcyclopentadiene.1,5

Variation of the pendant donor can also have a steric or electronic effect on the catalyst depending on the nature of the donor and its substituents. CGC pendant donors are typically neutral or monoanionic and are usually alkyl- or aryl-amido fragments.

However, several other groups such as phosphido,39 oxo,40 or pyrrolyl41 have been utilized. The donating ability of the pendant donor can affect the hapticity of the cyclopentadienyl moiety as transition metals tend to obey the eighteen-electron rule. The most common pendant donor used in constrained geometry catalysts is the monoanionic tert-butyl amido group.1,5

Constrained geometry catalysts can be synthesized by a variety of synthetic

42-44 4,45-48 40,49 routes. Amine elimination, salt metathesis, alkane elimination, Me3SiCl elimination,50,51 and HCl elimination52 have all been employed to synthesize CGC complexes. The two most widely used synthetic methods for preparing CGCs are salt metathesis by reaction of a lithiated ligand and a metal chloride, or amine elimination from a protonated ligand and metal-amido starting material. Amine elimination has proven to work quite well for cyclopentadienyl,43 substituted cyclopentadienyl,42 and indenyl moieties,44 but 5-fluorenyl moieties formed from amine elimination are still absent from the literature. This is presumably due to the lower acidity of the fluorenyl proton in the five-membered ring as well as increased sterics of the fluorenyl moiety.53

In some rare synthetic cases, a template approach54,55 is used wherein the cyclopentadiene moiety is initially attached to the metal precursor, then subsequent reaction with the cyclopentadienyl moiety to form a pendant donor is employed, thus forming the desired

CGC complex.

As mentioned in section 1.1, the earliest published constrained geometry complexes were by Shapiro and Bercaw,3 as well as Okuda.4 While these complexes were the first to be published in the open literature, a plethora of patents covering CGCs soon followed, the first of which were granted to Dow Chemical2 and Exxon Chemical56 in 1990. These patents described several derivatives of CGCs, all with the same general

CGC structure as detailed earlier, featuring monoanionic or dianionic ligands, and covering transition metals from groups four to ten. Dow and Exxon covered several bridging groups, cyclopentadienyl derivatives and pendant donors in their patents. The variety of complexes in these patents created the foundations for further research in constrained geometry catalysts. The research and alkene polymerization studies by Dow,

Exxon, Bercaw, and Okuda helped propel CGCs to a level of high interest for researchers in academia and industry over the past two decades.

1.6 Recent Constrained Geometry Catalysts

Several new constrained geometry catalysts have been synthesized by tailoring every aspect of the CGC structure. Though this research dates back to only 1990, a thorough search of scientific literature will produce a multitude of articles focused on

CGC‟s. The complexes featured in these articles are very diverse and have been prepared by a number of different synthetic methods40,47,48,52,57,58 (e.g. 8-13). It should be noted that a vast majority of constrained geometry complexes are composed of dianionic ligands, but there are some examples of monoanionic CGCs. CGCs are typically prepared from group 359 or group 41 metals, and most research focuses on titanium and

12 zirconium complexes, although complexes of group 5-8 metals5 have been reported as well.

Me Zr Me2Si Me2Si Me Zr N Ti Bz P NR2 O NR tBu Bz R 2 8 9 10

tBu P tBu Zr Cl Ti Me2Si N Cl Zr Cl t Cl N N Bu Cl Cl R tBu 11 12 13

Group 5 transition metal CGCs are known, but they are far outnumbered by group

4 complexes. Constrained geometry catalysts of vanadium have been synthesized in a variety of oxidation states. Complexes of V2+, V3+, V4+, and V5+ with a dianionic cyclopentadienyl-isopropylamido ligand with an ethylene bridge have been prepared (14-

17).60,61 A few other vanadium CGC complexes are known. Niobium and tantalum

CGCs have also been synthesized, but only in the +5 oxidation state (18a-b).62-65 Some

CGCs of later transition metals have been reported, but the examples are quite limited.

t V V PMe3 V Cl V N Bu Cl Cl Cl N N N N iPr iPr iPr iPr 14 15 16 17

NMe Me2Si M 2 N NMe2 NMe2 Ph 18a M = Nb 18b M =Ta

Group 6 CGC complexes of chromium(III),66 molybdenum(IV),67 molybdenum(V),50,51 molybdenum(VI),68 and tungsten(VI)68 are known. The only known group 7 complex contains of a rhenium(III)69,70 center, and the only example of a group 8 metal CGC of this type contains iron(II),4 though only spectroscopic characterization was used to determine the existence of this complex. CGC ligands of this type have also been employed in the synthesis of some group 13 complexes71,72 of aluminum, gallium, and indium, as well as some group 15 complexes73 of phosphorus, arsenic, and antimony. However, it should be noted that the group 13 and 15 complexes do not feature 5-coordination of the cyclopentadienyl moiety.

As seen in the group 4 and 5 examples and as reported in the group 6-8 complexes, anionic two-electron donors are widely used as the pendant group. Examples of nitrogen heterocycles are almost non-existent in the literature, which can be neutral or monoanionic two-electron pendant donors. The few reported CGC complexes utilizing nitrogen heterocycles as the pendant donor are limited to pyrrolyl41 (19, 21) and pyrazolyl59,74 (22) moieties. Furthermore, very few examples of trianionic CGC ligands are known in the scientific literature. The complexes that feature a trianionic ligand are composed of a cyclopentadienyl moiety with bridges in the 1- and 3-positions tethered to amido75 or pyrrolyl41 donors (20, 21). Pyrazolyl donor moieties have been utilized in a tridentate, monoanionic ligand by Otero et al. in some scandium, yttrium, and zirconium complexes.59,74 The group 3 complexes of this type have shown activity in ring-opening polymerization of -caprolactone.59

Me2Si SiMe2 Zr Ti Ti NMe N N N 2 N N tBu tBu NMe NMe2 Bz 2 19 20 21

Ph Ph

Cl NN Zr Cl N N Cl

A versatile library of CGC complexes is now accessible via various synthetic methods which allow derivatization at several locations of the complex. CGCs have been reported for group 3-8 transition metals, although group 4 complexes occupy the majority of known examples. Furthermore, dianionic ligands are the most widely utilized, though monoanionic and trianionic ligands have been used in some examples.

1.7 Transition Metal-Imido Complexes

Organoimido complexes of transition metals have been known for decades.76-78

These ligands have been employed in complexes of group 4 through 9 of the transition metal series, and have been utilized in various catalytic applications.77 Imido groups can have several binding modes; these moieties can form triple bonds (linear) or double bonds (bent) to a single metal and can also bridge two ( 2) or three ( 3) metal centers in binuclear or polymeric species. Formally, a terminal imido group, [NR]2 , is considered to be doubly bonded to a transition metal and is a four to six electron donor.6 Several experimental and computational studies have been performed to determine correlations

15 and energetics of the different binding modes. This has been done in relation to the hybridization of the imido nitrogen and electron donation of the imido moiety to the transition metal center. From these studies, several resonance forms have been proposed.77 No strict correlation has been found allowing for pre-determination of the binding mode in these complexes. Several factors can affect the imido group such as electron count on the transition metal and steric and electronic differences of the alkyl or aryl group on the imido nitrogen, as well as the number of imido ligands on the same metal center.

R R R R N N N N M M M M M M M linear bent 2 3

Terminal imido groups are well known for metals in high oxidation states (3+ and above) where the electron donation can stabilize metals with a low d-electron count.78

Imido ligands have considerable similarities to other ligands as they are valence isoelectronic with terminal oxo (M=O) ligands and are isolobal with 5-cyclopentadienyl

79 (C5R5 ) ligands. Furthermore, some imido complexes (depending on the ligand used) are isolobal analogues of metallocenes and ansa-metallocenes, giving them similarities to constrained geometry catalysts.

Transition metal imido (TMI) complexes have been of considerable interest due to their chemical reactivity. By varying the alkyl or aryl group on the imido nitrogen, more electron density can be placed on the imido nitrogen, thereby affecting chemical reactivity of TMI complexes. In some instances, imido complexes can activate C H bonds even so far as to activate methane, as demonstrated by some tantalum and

16 vanadium complexes by Wolczanski80 and Horton,81 respectively. Isoelectronic transition metal oxo complexes have also shown the ability to activate C H bonds, however, tailoring of the electronic and steric nature of the alkyl or aryl group on an imido ligand allows for more versatility and potentially more reactivity towards mediating reactions.

Imido chemistry of the transition metals has been explored for several decades, and by the end of the 1980‟s, imido chemistry of group 5 to 8 transition metals was well established.79 Examples of imido complexes of group 4 and 9 metals also began to appear around this time.82 Titanium imido complexes were not structurally characterized until Rothwell et al.83 and Roesky et al.84 reported some five-coordinate (23) and six- coordinate (24) complexes, respectively. Stephan et al. have recently reported some closely related phosphinimine compounds (25) as well.85

Ph S t Ph N P Ph P Bu3 N N N py' = Cl Cl py Ti Ti Ti N Ti py' OAr py Cl Cl ArO py' py N t i Bu 3P 23 Ar = 2,6- Pr2C6H3 24 25

Zirconium imido complexes analogous to the titanium complexes are not as well defined and are mostly dimeric, although there are some examples that are monomeric.86

Typically, aryl- and alkylimido complexes of zirconium tend to be dimeric with imido groups bridging two zirconium centers like in complexes 26 and 27. However, treatment

i of the THF adduct [Zr2( -N-2,6- Pr2C6H3)2Cl4(THF)4] with excess pyridine will produce a monomeric zirconium imido complex (28). Monomeric species are not formed from the 2,6-dimethylphenyl- and alkylimido THF adducts upon treatment with pyridine, as

17 they still produce the dimeric species [Zr2( -N-2,6-Me2C6H3)2Cl4(py)4] and [Zr2( -

t N Bu)2Cl4(py)3] respectively.

R Ar Ar Cl Cl Cl Cl THF N THF N THF N Zr Zr THF Zr Zr Cl py THF N THF N THF Zr Cl Cl Cl Cl py Cl R Ar py t i i i R = Bu, Pr, CH2Ph Ar = 2,6- Pr2C6H3, 2,6-Me2C6H3 Ar = 2,6- Pr2C6H3 26 27 28

Group 4 and 5 imido complexes have been prepared and studied by several research groups including those of Mountford,87-89 Odom,90,91 Cummins,91,92 and

Arnold.93-95 Specifically, some titanium imido dichloride species have been used to synthesize a variety of metal-imido complexes with triazacyclononane ligands, 5- cyclopentadienyl ligands79 (29), amidinate ligands79 (30), tris(pyrazolyl)borate ligands,96 diamidoamine and diamidopyridine ligands87 (31), as well as triazamacrocycle ligands.88

tBu N NtBu py Cl Me3Si Ti Ti N N py N N Ti NtBu N Me3Si N SiMe3 py Me3Si 29 30 31

In recent years, several attempts have been made to study the reactivity of transition metal imido complexes. To achieve this, the imido fragment nneds to be stabilized enough to isolate monomeric metal complexes, but still allow enough access to the metal center for reactivity studies of the imido moiety.79 This method can be pursued though multidentate ligands that are neutral, monoanionic, or dianionic. Several imido compounds with multidentate ligands have been reported in the literature. Interestingly,

18 compounds like 32 and 33 are isolobal analogues of their corresponding metallocene and ansa-metallocene derivatives, respectively, linking these compounds to the constrained geometry catalysts.97

Me N N N N N N Me Nb Me Me Ti Cl t Cl N Cl N Bu Cl 32 33

1.8 Research Statement

From the sections described in this chapter, one can see the utility of constrained geometry catalysts in various catalytic applications. It is clear that group 4 transition metals are useful as constrained geometry catalysts that produce polymers of desired tacticity. New complexes of group 5 and 6 metals with trianionic ligands could provide very active catalysts in the polymerization of alkenes. The sterically crowded metal center and adjustable symmetry could enable great control over tacticity.

Early investigations by the Mason research group of some titanium and zirconium complexes featuring di(3-methylindolyl)methane ligands resulted in catalysts with low ethylene polymerization activity.98 A potential explanation for the low activity is ligand transfer to the activating agent.99 For these reasons, trianionic 3-methylindole and pyrrole based ligands with one 5-cyclopentadienyl moiety have been developed and investigated for use in the synthesis of constrained geometry complexes with group 4 and

5 transition metals. Ligands based on 3-methylindolyl and pyrrolyl donor groups should produce metal complexes with Lewis acidic metal centers, making them attractive for

19 catalytic applications such as alkene polymerization. The use of an 5-cyclopentadienyl group in this new set of ligands should circumvent the issue of ligand transfer, and result in catalysts with higher activities. These complexes are structurally similar to the zirconium complex reported by Otero et al.74 To our knowledge, the only published tridentate, trianionic ligands used in constrained geometry complexes are those of Seo et al. and Cano et al.41,75 CGCs of group 4 and 5 metals with trianionic 3-methylindole and pyrrole based ligands should have an electrophilic metal center, making them attractive for catalytic use.

Recent work in the Mason research group has also centered on a series of di(3- methylindolyl)methane ligands with one neutral, aromatic donor.100,101 Early investigations by Fneich102 with these ligand systems produced some titanium and zirconium biscyclopentadienyl101 and bis(dialkylamido)98 complexes for use as ethylene polymerization catalysts. The ligands in the Mason group complexes feature two monoanionic 3-methylindolyl moieties as well as a non-coordinating group, such as phenyl and 4-bromophenyl, or neutral two-electron donors including 2-pyridyl (34) and

2-methoxyphenyl (35) groups. Later, this ligand set was expanded by Das103 to include

N-methylimidazole (36) as the neutral donor. These ligands were used in some aluminum and gallium complexes that targeted carbon monoxide coordination to the

Lewis acidic metal center for reactivity studies.

OCH3 H

N N CH3 H NH HN N H

35 NH HN NH HN

34 36

The di(3-methylindolyl)methane ligands pose an interesting framework with which to synthesize group 4 imido complexes. Group 4 transition metal-imido complexes have been demonstrated in the literature to be useful complexes in catalytic chemistry.79 Use of the di(3-methylindolyl)methane framework would produce complexes analogous to the {bis(trimethylsilylamido)pyridyl}titanium complex (31)

87 reported by Mountford and coworkers. These complexes should be stable, 10 to

12 electron compounds; the metal center is in the 4+ oxidation state with two monoanionic 3-methylindolyl moieties bonded to the metal, an imido moiety, and one neutral two-electron donor coordinated (e.g. 37, 38, 39). There should be ample space for substrates to coordinate, facilitating further reactivity.

R R R

N N N CH3 M M M O N N N N N N N N N

H H H 37 38 39

M = Ti, Zr R = alkyl, aryl

This dissertation reports transition metal complexes of group 4 and 5 transition metals with potential applications in alkene polymerization and hydroamination, although catalytic applications could reach well beyond these two uses. Chapter two discusses the ligand design for the constrained geometry complexes, and details their preparation and characterization. Chapter three discusses the formation of CGC complexes of group 4 and 5 transition metals with trianionic 3-methylindolyl- or pyrrolyl-based ligands. These complexes represent the first constrained geometry complexes of group 4 and 5 metals with trianionic indole-based ligands. Chapter three also details the initial formation of group 4 imido complexes of di(3-methylindolyl)methane ligands, and discusses their characterization and potential catalytic applications. Chapter four details a research project conducted under the guidance of Dr. Bruce A. Averill, and discusses a series of copper(I) pyridine derivative complexes aimed at efficient separation of ethylene and propylene in a mixture of olefins. These complexes could reduce the energy and financial costs of current systems in use. Appendix 1 reports an initial project that was conducted at the beginning of my research in Dr. Mason‟s group, and details the synthesis and characterization of metallophosphinate complexes of aluminum and gallium. This appendix also reports reactions of triphenylaluminum and triphenylgallium with phosphonic acids. Products isolated in these reactions were difficult to characterize due to their insoluble nature and amorphous composition. These types of materials are believed to have potential use in catalytic and molecular sieve applications.

Chapter Two

Trianionic Indole- and Pyrrole-Based Constrained Geometry Ligands

2.1 Introduction

Developments in ansa-metallocene chemistry led to the creation of constrained geometry catalysts (CGC).2-4,56 Constrained geometry complexes were first synthesized by replacing one cyclopentadienyl moiety of ansa-metallocenes with a pendant amido donor group. Several ligand variations have been explored in constrained geometry systems since, though virtually all examples feature one 5-moiety and one or two pendant donor groups.1,5 These ligands are typically mono- or dianionic in nature, and reports of trianionic ligands are essentially non-existent.41,75,104 Currently, the only known examples in the literature of trianionic constrained geometry ligands are compounds 4075 and 41.41 To our knowledge, only one set of constrained geometry ligands exhibit monoanionic nitrogen heterocycles as the pendant donor group (41, 42,

43).41,105 Constrained geometry ligands have gained interest since their initial discovery particularly due to the „constrained‟ angle imposed by tethering two groups of the ligand, which exposes the metal center but also allows the catalysts to maintain their structure throughout the catalytic process. These advantages typically result in a more active alkene polymerization catalyst.

t t BuNH HN Bu NH HN NH NH

40 41 42 43

Early ligand systems were developed using alkylated cyclopentadiene moieties, dimethylsilyl bridges, and tert-butylamido pendant donors.2-4,56 The general CGC ligand structure can be modified in three distinct areas: 1) the cyclopentadiene moiety, 2) the bridge (Z), and 3) the pendant donor (E) (Figure 2.1). The cyclopentadienyl moiety has been exchanged with other 5-coordinating species such as fluorenyl or indenyl moieties.

The bridge has been modified with carbon chains, phosphorus, or boron derivatives. The pendant donor has been modified with several amido, phosphido, or sulfido groups, as well as some other donors. These ligand modifications have been explored to induce steric, electronic, and stereochemical changes within the catalyst system.

alkylated cyclopentadiene cyclopentadiene indene Z fluorene

SiR2 E CR2 NHAr NHR C2R4 C R PHAr 3 6 PHR PR OH BR SH "C"

Figure 2.1. Typical constrained geometry ligand structure.

The versatility of the constrained geometry ligands is mirrored in the plethora of metal complexes that have been prepared using this framework. These ligands can be tailored to fit a variety of transition metals. Complexes of early metals such as scandium and zirconium have been prepared as well as some complexes of mid to late metals such as molybdenum,67 rhenium,69 and nickel.106 A few main group metal constrained geometry complexes have also been prepared with aluminum, though it should be noted that the cyclopentadiene moiety does not exhibit 5-coordination to the aluminum center.71-73

Ligands featuring indolyl,98,101,107-109 pyrrolyl,41,110-112 or pyrazolyl59,74,96 moieties have proven to be quite useful in the formation of transition metal complexes. In comparison to the strong electron donation of amido groups, which are typically used in

CGC complexes, indolyl moieties are believed to be electron withdrawing and less - donating due to delocalization of the nitrogen lone pair in the aromatic system.113 This feature makes indoles attractive for use in catalyst preparation since they are less prone to

M N M bridging, resulting in the formation of monometallic species. Furthermore, reduced electron donation could result in a more Lewis acidic metal center, and therefore a more active catalyst. These advantages have been explored with some group 4 metal complexes of di(3-methylindolyl)methanes by the Mason group.98,101,102 Utilizing a di(3- methylindolyl)- or dipyrrolyl- framework with the addition of an 5-cyclopentadienyl moiety is expected to stabilize the metal center and help maintain catalyst structure throughout the catalytic process. A ligand structure (44a, 44b) similar to this has been reported by Otero et al. to generate scandium (45a, 45b), yttrium (46a, 46b), and zirconium (47) complexes. Therefore, a ligand system based on two monoanionic

25 indolyl- or pyrrolyl- moieties will result in a trianionic ligand and potentially form group

IV and V transition metal complexes. These complexes could be useful for alkene polymerizations and copolymerizations, and should be structurally analogous to the complexes reported by Otero et al.

R' R

N N N N

R = R' = Ph 44a R = tBu, R' = H 44b

R' Ph R Ph

M CH SiMe Cl NN 2 3 N N Zr Cl N N N N CH2SiMe3 Cl

R = R' = Ph; M = Sc (45a), Y (46a) 47 R = tBu, R' = H; M = Sc (45b), Y (46b)

In this chapter, the synthesis and characterization of diethyl acetals and indolyl- and pyrrolyl-based ligands for use in constrained geometry complexes is described.

Specifically, diethyl acetals with fluorenyl (48), indenyl (49), and cyclopentadienyl (50) moieties are used as precursors for the synthesis of the constrained geometry ligands fluorenyl di(3-methylindolyl)ethane (51), fluorenyl dipyrrolylethane (52), indenyl di(3- methylindolyl)ethane (53), and indenyl dipyrrolylethane (54). Initial attempts to generate di(3-methylindolyl)- or dipyrrolyl- ligands with cyclopentadienyl acetaldehyde diethylacetal are also discussed (55, 56).

CH(OCH2CH3)2 CH(OCH2CH3)2 CH(OCH2CH3)2 CH(OCH2CH3)2 1,2-isomer 1,3-isomer

48 49 50

H H H N NH

NH NH

51 52

H H H N NH

NH NH

53 54

H H H N NH

NH NH

55 56

2.2 Experimental

General Procedures

All air- and moisture-sensitive reactions were performed in an inert atmosphere of purified nitrogen using standard inert atmosphere techniques and an Innovative

Technologies dry box. Methylene chloride and methanol were purchased from Fisher

Scientific and used as received. Toluene was distilled from sodium, hexanes and acetonitrile were distilled from calcium hydride, and diethyl ether and tetrahydrofuran were distilled from sodium benzophenone ketyl prior to use. Pyrrole was purchased from

Aldrich and distilled from calcium hydride. Fluorene, indene, dicyclopentadiene, bromoacetaldehyde diethylacetal, 3-methylindole, and zirconium(IV) chloride were purchased from Aldrich and used without further purification. Chloroform-d and benzene-d6 were dried by storage over activated molecular sieves. Solution NMR spectra were recorded on a Varian Inova 600 spectrometer. Chemical shifts are reported relative to TMS. 1H and 13C NMR assignments were aided by 2D-COSY and 2D-HMQC and

2D-HMBC experiments. Low-resolution mass spectral m/z values were recorded on a

Bruker Esquire-LC Mass Spectrometer with a sodium or potassium ionization source and are reported for the predominant peak in the isotope pattern. Elemental analyses were performed by The College of Arts and Sciences Instrumentation Center at The University of Toledo.

4 4 4 3 3 3a 3 5 3a 4a 5 2 2 2 6 7a N 1 6 1a 1 7a 1 7 H 9 7

Figure 2.2. Numbering schemes for indole, fluorene, and indene, respectively.

Preparation of fluorenyl acetaldehyde diethylacetal (48)

Fluorene (26.8 g, 0.161 mol) was dissolved in 200 mL of diethyl ether. To this, a solution of nBuLi in hexanes was added dropwise (100 mL, 1.6 M, 0.161 mol) at 0 °C.

The reaction solution turned orange, and was warmed to 25 °C for 30 min. This solution was added dropwise to a solution of bromoacetaldehyde diethylacetal (31.8 g, 25.0 mL,

0.161 mol) in 50 mL of diethyl ether at 0 °C. The reaction mixture turned purple after warming to 25 °C and was stirred for 12 h. Volatiles were removed in vacuo leaving a purple oil. 300 mL of methylene chloride was added, the reaction mixture turned cloudy white. It was extracted with 5 100 mL portions of deionized water. The yellow organic layer was separated and dried over anhydrous Na2SO4. Volatiles were removed from the dried solution in vacuo, resulting in a pale yellow oil, which solidified to a

1 yellow waxy solid upon standing. Yield: 42.2 g, 0.149 mol, 93%. H NMR (CDCl3, 600

3 3 MHz): 7.73 (d, JHH = 7.8 Hz, 2H, flu-H4), 7.54 (d, JHH = 7.8 Hz, 2H, flu-H1), 7.34 (t,

3 3 3 JHH = 7.2 Hz, 2H, flu-H3), 7.28 (t, JHH = 7.2 Hz, 2H, flu-H2), 4.69 (t, JHH = 6.0 Hz,

3 1H, CH), 4.08 (t, JHH = 7.2 Hz, 1H, flu-CH), 3.52 (dm, 4H, OCH2CH3), 2.21 (dd, 2H,

3 13 1 CH2), 1.13 (t, JHH = 7.2 Hz, 6H, OCH2CH3). C{ H} NMR (CDCl3, 150.8 MHz):

147.25 (s, C1a), 140.81 (s, C4a), 126.96 (s, C2), 126.82 (s, C3), 124.73 (s, C1), 119.78 (s,

C4), 101.41 (s, CH), 61.45 (s, OCH2CH3), 43.93 (s, C9), 37.49 (s, CH2), 15.27 (s,

OCH2CH3). MS (ES) m/z (assignment, relative intensity): 305.2 (C19H22O2Na, [M +

+ Na] , 100%). Anal. Calcd. for C19H22O2: C, 80.82; H, 7.85. Found: C, 80.89; H, 8.09.

Preparation of indenyl acetaldehyde diethylacetal (49)

Indene (5.35 g, 32.2 mmol) was dissolved in 50 mL of diethyl ether. A solution of n-butyllithium in hexanes was added dropwise (20 mL, 1.6 M, 32 mmol) at 0 °C. The reaction solution turned yellow, and was warmed to 25 °C for 30 min. This mixture was added dropwise to a solution of bromoacetaldehyde diethylacetal (6.35 g, 5.00 mL, 32.2 mmol) in 50 mL of diethyl ether at 0 °C. The reaction mixture turned bright red after warming to 25 °C and was stirred for 12 h, during which time it turned brown. Volatiles were removed in vacuo, leaving a brown oil. After addition of 100 mL of methylene chloride, the reaction mixture turned cloudy white, and was extracted with 3 100 mL portions of deionized water. The brown organic layer was separated and dried over anhydrous Na2SO4. The solvent was removed from the dried solution in vacuo, resulting

1 in a brown oil. Yield: 5.48 g, 23.5 mmol, 85%. H NMR (CDCl3, 600 MHz): 7.43 (d,

3 3 3 JHH = 7.2 Hz, 1H, H4), 7.35 (d, JHH = 7.8 Hz, 1H, H7), 7.25 (t, JHH = 7.2 Hz, 1H, H5),

3 7.19 (t, JHH = 7.2 Hz, 1H, H6), 6.80 (dd, 1H, H2), 6.61 (dd, 1H, H3), 4.68 (m, 1H, CH),

3.69 (dm, 2H, OCH2CH3), 3.56 (m, 1H, H1), 3.52 (dm, 2H, OCH2CH3), 2.22 (m, 1H,

3 3 CH2), 1.71 (m, 1H, CH2), 1.24 (t, JHH = 7.2 Hz, 3H, OCH2CH3), 1.19 (t, JHH = 7.2 Hz,

13 1 3H, OCH2CH3). C{ H} NMR (CDCl3, 150.8 MHz): 147.51 (s, C7a), 144.13 (s, C3a),

139.13 (s, C3), 130.79 (s, C2), 126.56 (s, C5), 124.73 (s, C6), 123.00 (s, C4), 121.05 (s,

C7), 102.10 (s, CH), 61.44 (s, OCH2CH3), 61.23 (s, OCH2CH3), 46.66 (s, C1), 35.51 (s,

CH2), 15.38 (s, OCH2CH3). MS (ES) m/z (assignment, relative intensity): 255.2

+ (C15H20O2Na, [M + Na] , 100%). Anal. Calcd. for C15H20O2: C, 77.54; H, 8.68. Found:

C, 77.34; H, 8.76.

Preparation of cyclopentadienyl acetaldehyde diethylacetal (50)

Cyclopentadienyl acetaldehyde diethylacetal was prepared using modified literature procedures.114,115 Sodium hydride (2.0 g, 60% wt. dispersion in mineral oil, 5.0

101 mmol) was stirred in 40 mL of hexanes. Hexanes were decanted, and 35 mL of

THF was added via dropping funnel. A solution of freshly cracked cyclopentadiene (10 mL) in 10 mL THF was added dropwise. The resulting pink mixture was added dropwise to a solution of bromoacetaldehyde diethylacetal (7.80 mL, 9.90 g, 50.0 mmol) in 45 mL

THF, creating a brown solution and white precipitate. The mixture was stirred for 12 h at

25 °C, filtered over Celite to remove sodium bromide, and concentrated to a brown oil in vacuo. To this was added 50 mL of dichloromethane, and the mixture was filtered through Celite to remove remaining sodium bromide. Volatiles were removed in vacuo, leaving a brown oil. 1H NMR data suggests a 1:1 mixture of 1,2- and 1,3- isomers by

114 1 comparison to reported NMR data. H NMR (CDCl3, 600 MHz): 6.50 (m, 1H, olefin), 6.43 (m, 1H, olefin), 6.40 (m, 1H, olefin), 6.29 (m, 1H, olefin), 6.27 (m, br, 1H, olefin), 6.14 (m, br, 1H, olefin), 4.66 (t, 1H, CH), 4.61 (t, 1H, CH), 3.67 (m, 4H,

CH2CH3), 3.51 (m, 4H, CH2CH3), 2.96 (m, 2H, CH2), 2.75 (d, 1H, CH2, Cp ring), 2.72 (d,

13 1 1H, CH2, Cp ring) 1.21 (t, 12H, CH2CH3). C{ H} NMR (CDCl3, 150.8 MHz): 144.16

(s), 142.05 (s), 135.01 (s), 133.47 (s), 132.30 (s), 131.54 (s), 128.68 (s), 128.51 (s),

102.72 (s), 102.52 (s), 61.26 (s), 61.08 (s), 44.07 (s), 41.33 (s), 35.24 (s), 34.62 (s), 15.30

(s).

Preparation of fluorenyl di(3-methylindolyl)ethane (51): Method 1

Fluorenylacetaldehyde diethylacetal (48) (4.00 g, 14.2 mmol) and 3-methylindole

(3.72 g, 28.4 mmol) were dissolved in 10 mL of methanol and stirred at 25 °C for 15 min.

A catalytic amount of concentrated sulfuric acid (0.200 mL) was added via syringe. The reaction solution turned dark yellow and was warmed to 40-45 °C for 12 h. The brown reaction mixture was cooled to 25 °C, and 20 mL of methanol was added. An aqueous solution of sodium bicarbonate (20 mL, 1.0 M) was added and the reaction mixture turned cloudy and was stirred for 30 min. After addition of 50 mL of methylene chloride, the solution was extracted with 3 100 mL of deionized water. The yellow organic layer was separated and dried over anhydrous Na2SO4. The solution was concentrated in vacuo and placed in a freezer ( 30 °C) overnight. A pale yellow microcrystalline solid was isolated by filtration and washed with cold methylene chloride. X-ray quality crystals were obtained from a concentrated toluene/THF solution. Yield: 3.86 g, 8.53 mmol,

1 3 60%. H NMR (CDCl3, 600 MHz): 7.69 (s, broad, 2H, NH), 7.66 (d, JHH = 7.8 Hz,

3 3 2H, indo-H7), 7.47 (d, JHH = 7.8 Hz, 2H, flu-H4) 7.43 (d, JHH = 7.8 Hz, 2H, indo-H4),

3 3 3 7.26 (t, JHH = 7.2 Hz, 2H, indo-H6), 7.21 (d, JHH = 7.8 Hz, 2H, flu-H1), 7.19 (t, JHH =

3 3 7.8 Hz, 2H, flu-H3), 7.12 (t, JHH = 7.2 Hz, 2H, flu-H2), 7.07 (t, JHH = 7.2 Hz, 2H, indo-

3 3 H5), 4.75 (t, JHH = 7.2 Hz, 1H, CH), 4.00 (t, JHH = 7.2 Hz, 1H, flu-CH), 2.72 (dd, 2H,

13 1 CH2), 2.12 (s, 6H, CH3). C{ H} NMR (CDCl3, 150.8 MHz): 146.30 (s, C1a), 140.95 (s,

C4a), 135.35 (s, C7a), 133.93 (s, C3a), 129.48 (s, indo-C2), 127.12 (s, C6), 126.79 (s, flu-

C3), 124.00 (s, flu-C4), 121.56 (s, flu-C2), 119.85 (s, C7), 119.34 (s, indo-C5), 118.31 (s, indo-C4), 110.64 (s, flu-C1), 108.20 (s, indo-C3), 45.67 (s, flu-C9), 37.68 (s, CH2), 32.82

(s, CH), 8.74 (s, CH3). MS (ES) m/z (assignment, relative intensity): 491.1 (C33H28N2K,

+ [M + K] , 100%). Anal. Calcd. for C33H28N2•C4H8O: C, 84.93; H, 6.92; N, 5.19. Found:

C, 84.68; H, 7.09; N, 5.38.

Preparation of fluorenyl di(3-methylindolyl)methane (51): Method 2

Fluorenylacetaldehyde diethylacetal (48) (1.13 g, 4.00 mmol) and 3-methylindole

(1.05 g, 8.01 mmol) were dissolved in 15 mL of acetonitrile and stirred at 25 °C for 15 min. A solution of ZrCl4 (0.100 g, 0.40 mmol) in 10 mL acetonitrile was added via cannula. The reaction solution turned brown and was stirred at 25 °C for 12 h. Then, 25 mL of deionized water were added and the mixture was stirred for 30 min. The brown reaction mixture was extracted with 3 50 mL ethyl acetate, and the combined organic portions were dried over anhydrous Na2SO4. The resulting decantate was evaporated to dryness via rotary evaporation, and the resulting residue was purified by column chromatography (silica gel, 20% methylene chloride in hexanes). The resulting yellow residue was dried in vacuo. Yield: 1.07 g, 2.36 mmol, 59%.

Preparation of fluorenyl dipyrrolylethane (52)

Fluorenylacetaldehyde diethylacetal (48) (1.13 g, 4.00 mmol) was dissolved in 10 mL of acetonitrile. A solution of pyrrole (1.10 mL, 1.07 g, 16.0 mmol) in 5 mL acetonitrile was added and the mixture was stirred at 25 °C for 15 min. A solution of

ZrCl4 (0.100 g, 0.400 mmol, 10 mol%) in 10 mL acetonitrile was added via cannula. The reaction solution turned brown, and was stirred at 25 °C for 12 h. Addition of 25 mL of deionized water and stirring for 30 minutes resulted in a brown reaction mixture, which was extracted with 3 50 mL portions of ethyl acetate. The combined organic portions

33 were dried over anhydrous Na2SO4. Volatiles were removed via rotary evaporation, and the resulting brown residue was purified by column chromatography (silica gel, 20% methylene chloride in hexanes). The resulting light brown solid was dried in vacuo.

1 3 Yield: 0.37 g, 1.1 mmol, 28%. H NMR (CDCl3, 600 MHz): 7.74 (d, JHH = 7.2 Hz,

3 3 2H, flu-H4), 7.63 (s, broad, 2H, NH) 7.43 (d, JHH = 7.2 Hz, 2H, flu-H1), 7.34 (t, JHH =

3 7.2 Hz, 2H, flu-H3), 7.26 (t, JHH = 7.2 Hz, 2H, flu-H2), 6.57 (q, 2H, pyrr-H5), 6.12 (q,

3 3 2H, pyrr-H4), 6.09 (m, broad, 2H, pyrr-H3), 4.38 (t, JHH = 7.8 Hz, 1H, CH), 3.90 (t, JHH

3 13 1 = 6.6 Hz, 1H, flu-CH), 2.44 (t, JHH = 7.8 Hz, 2H, CH2). C{ H} NMR (CDCl3, 150.8

MHz): 147.40 (s, C1a), 140.78 (s, C4a), 132.77 (s, pyrr-C2), 126.97 (s, flu-C3), 126.83

(s, flu-C2), 124.50 (s, flu-C1), 119.84 (s, flu-C4), 117.35 (s, pyrr-C5), 108.16 (s, pyrr-

C4), 105.94 (s, pyrr-C3), 45.24 (s, flu-C9), 39.34 (s, CH2), 35.93 (s, CH). MS (ES) m/z

+ (assignment, relative intensity): 346.8 (C23H20N2Na, [M + Na] , 100%). Anal. Calcd. for

C23H20N2: C, 85.15; H, 6.21; N, 8.64. Found: C, 84.22; H, 6.42; N, 7.86.

Preparation of indenyl di(3-methylindolyl)ethane (53)

Indenyl acetaldehyde diethylacetal (49) (0.938 g, 4.00 mmol) was dissolved in 15 mL of acetonitrile. The solution was transferred via cannula to a flask containing 3- methylindole (1.05 g, 8.00 mmol). A solution of ZrCl4 (0.095 g, 0.40 mmol, 10 mol%) in

10 mL of acetonitrile was added. The reaction mixture turned dark brown and was stirred at 25 °C for 12 h. After addition of 20 mL of deionized water, then the mixture was extracted with 3 50 mL portions ethyl acetate. The brown organic layer was separated and dried over anhydrous Na2SO4. After filtration volatiles were removed via rotary evaporation. The resulting brown residue was dissolved in a minimal amount of a 1:1

34 mixture of methylene chloride and hexanes, and purified by column chromatography

(silica gel, 20% methylene chloride in hexanes). Volatiles were removed via rotary evaporation, leaving a yellow solid that was dried in vacuo. Yield: 1.09 g, 2.71 mmol,

1 67%. H NMR (CDCl3, 600 MHz): 7.85 (s, broad, 1H, NH), 7.79 (s, broad, 1H, NH)

3 3 3 7.53 (d, JHH = 7.8 Hz, 2H, indo-H7), 7.49 (d, JHH = 7.8 Hz, 2H, indo-H7) 7.39 (d, JHH

3 3 = 7.2 Hz, 2H, inde-H4), 7.34 (d, JHH = 7.2 Hz, 2H, indo-H4), 7.28 (d, JHH = 7.8 Hz, 2H,

3 3 indo-H4), 7.24 (t, JHH = 7.2 Hz, 1H, indo-H6), 7.23 (d, JHH = 7.2 Hz, 2H, inde-H7),

3 3 3 7.16 (t, JHH = 7.2 Hz, 1H, indo-H5), 7.15 (t, JHH = 7.2 Hz, 1H, indo-H6), 7.13 (t, JHH =

3 3 7.2 Hz, 1H, indo-H5), 7.12 (t, JHH = 7.2 Hz, 1H, inde-H5), 7.09 (t, JHH = 7.2 Hz, 1H, inde-H6), 6.75 (dd, 1H, inde-H2), 6.39 (dd, 1H, inde-H3), 4.76 (dd, 1H, CH), 3.44 (m,

1H, inde-H1), 2.74 (m, 1H, CH2), 2.33 (s, 3H, CH3), 2.23 (s, 3H, CH3), 2.18 (m, 1H,

13 1 CH2). C{ H} NMR (CDCl3, 150.8 MHz): 147.01 (s, inde-C7a), 144.04 (s, inde-C3a),

137.75 (s, inde-C3), 135.53 (s, indo-C7a), 135.19 (s, indo-C7a), 134.38 (s, indo-C3a),

134.04 (s, indo-C3a), 131.61 (s, inde-C2), 129.60 (s, indo-C2), 129.44 (s, indo-C2),

126.82 (s, inde-C7), 124.93 (s, indo-C5), 122.69 (s, inde-C4), 121.79 (s, indo-C5), 121.63

(s, indo-C6), 121.26 (s, indo-C4), 119.47 (s, inde-C6), 118.50 (s, indo-C7), 118.36 (s, indo-C7), 110.73 (s, indo-C4), 110.68 (s, indo-C6), 110.68 (s, inde-C5), 108.56 (s, indo-

C3), 107.98 (s, indo-C3), 48.61 (s, inde-C1), 36.24 (s, CH2), 34.36 (s, CH), 8.96 (s, CH3),

8.80 (s, CH3). MS (ES) m/z (assignment, relative intensity): 441.0 (C29H26N2K, [M +

+ K] , 100%).

Preparation of indenyl dipyrrolylethane (54)

Indenylacetaldehyde diethylacetal (49) (0.93 g, 4.0 mmol) and pyrrole (1.10 mL,

1.07 g, 16.0 mmol) were dissolved in 15 mL acetonitrile and stirred at 25 °C for 15 min.

A solution of ZrCl4 (0.10 g, 0.40 mmol, 10 mol%) in 10 mL acetonitrile was added via cannula. The reaction solution turned brown and was stirred at 25 °C for 12 h. After addition of 25 mL of deionized water, the mixture was extracted with 3 50 mL portions of ethyl acetate. The combined organic portions were dried over anhydrous Na2SO4.

Volatiles were removed by rotary evaporation, and the resulting brown residue was purified by column chromatography (silica gel, 20% methylene chloride in hexanes).

The resulting light brown solid was dried in vacuo. Yield: 0.188 g, 0.721 mmol, 18%.

1 H NMR (CDCl3, 600 MHz): 7.71 (s, broad, 1H, NH), 7.66 (s, broad, 1H, NH), 7.43 (d,

3 3 3 JHH = 7.2 Hz, 1H, inde-H4), 7.38 (d, JHH = 7.2 Hz, 1H, inde-H7), 7.29 (t, JHH = 7.8 Hz,

3 3 1H, inde-H5), 7.23 (t, JHH = 7.8 Hz, 1H, inde-H6), 6.80 (d, JHH = 5.4 Hz, 1H, inde-H2),

3 6.66 (m, 1H, pyrr-H5), 6.62 (m, 1H, pyrr-H5), 6.36 (d, JHH = 5.4 Hz, 1H, inde-H3), 6.22

(m, 1H, pyrr-H4), 6.20 (m, 1H, pyrr-H4), 6.19 (m, 1H, pyrr-H3), 6.13 (m, 1H, pyrr-H3),

13 4.27 (dd, 1H, CH), 3.43 (m, 1H, inde-H1), 2.53 (m, 1H, CH2), 2.02 (m, 1H, CH2). C

NMR (CDCl3, 151 MHz): 147.56 (s, C7a), 144.06 (s, C3a), 138.63 (s, inde-C3), 133.13

(s, pyrr-C2), 132.53 (s, pyrr-C2), 130.86 (s, inde-C2), 126.57 (s, inde-C5), 124.70 (s, inde-C6), 122.84 (s, inde-C4), 121.07 (s, inde-C7), 117.45 (s, pyrr-C5), 117.31 (s, pyrr-

C5), 108.14 (s, pyrr-C4), 108.13 (s, pyrr-C3), 106.27 (s, pyrr-C4), 105.61 (s, pyrr-C3),

48.40 (s, inde-C1), 36.92 (s, CH), 36.62 (s, CH2). MS (ES) m/z (assignment, relative

+ intensity): 312.9 (C18H17N2K, [M + K] , 100%). Anal. Calcd. for C18H17N2: C, 83.22; H,

6.61; N, 10.21. Found: C, 83.22; H, 6.98; N, 9.17.

2.3 X-Ray Crystallography

Crystals of 51·THF were grown from a concentrated THF/toluene solution stored at 30 °C. The X-ray diffraction data were collected on a Siemens three-circle platform diffractometer equipped with a 4K CCD detector. The frame data were collected with the SMART 5.625116 software using Mo K radiation ( = 0.71073 Å).

Cell constants were determined with SAINT 6.22117 from the complete data set. A complete hemisphere of data was collected using (0.3°) scans with a run time of 30 s/frame at different angles. A total of 1415 frames were collected for the dataset. An additional 50 frames, identical to the first 50, were collected to determine crystal decay.

The frames were integrated using the SAINT 6.22 software, and the data were corrected for absorption and decay using the SADABS118 program. The structure was solved by direct methods and refined by least-squares methods on F2, using the SHELXTL program suite.119 The THF molecule in the crystal structure of 51 was disordered, and was modeled by locating the non-hydrogen atoms from the difference fourier map. There are three THF molecules with different occupancies of 0.45, 0.30, and 0.25. The model used was refined with constraints on the bond distances and atomic displacement parameters.

Details of data collection and refinement are provided in Table 2.1. Further details, including atomic coordinates, distances and angles are found in the CIF files in Appendix

Table 2.1. Crystal data and structure refinement details for compound 51·THF ______

Formula C37H36N2O temp, °C 133 Fw 524.7 μ, mm-1 0.071 Cryst. Syst monoclinic λ, Å 0.7107

Space group P21/n transm coeff 1.00-0.837 a, Å 10.5616(10) 2θ limits, deg 4.10 to 51.98 b, Å 9.5966(9) total no. of data 16039 c, Å 28.719(3) no. unique data 5441 α, deg 90.00 no. obsd dataa 4828 β, deg 90.592(2) no. of params 481 b γ, deg 90.00 R1 (I > 2σ(I)) 0.0571 3 2 c V, Å 2910.7(5) wR2 (I , all data) 0.1435 Z 4 max, min peaks, e/Å3 0.350, 0.410 -3 Dcalcd, g cm 1.197 ______a b c 2 2 2 2 2 1/2 I > 2σ(I). R1 = | |Fo| – |Fc| | / |Fo|. wR2 = [ [w (Fo – Fc ) ] / [w (Fo ) ]] .

2.4 Results and Discussion

In the initial stages of this project, there were two synthetic routes envisioned towards the synthesis of indole- and pyrrole-based constrained geometry ligands. The first synthetic route was to react bromoacetaldehyde diethylacetal with two equivalents of either 3-methylindole or pyrrole via acid-catalyzed condensation (eq. 1).

H H Br N H acid catalyst N (1) + 2

CH(OEt)2 HN

This method would allow for simple transformation of this product to a constrained geometry ligand via N-protection and reaction with a lithiated cyclopentadienyl moiety.

Several attempts were made to synthesize bromo(di(3-methylindolyl))ethane with catalysts such as concentrated sulfuric acid or zirconium tetrachloride. These syntheses were unsuccessful at room temperature or elevated temperatures, or in various solvents including ethanol, methanol, acetonitrile, or methylene chloride. Similar reaction conditions were employed for attempted synthesis of bromo(dipyrrolyl)ethane, with trifluoroacetic acid or zirconium chloride as acid catalysts. Again, syntheses under these conditions were unsuccessful. Changes in temperature (ambient, reflux) or solvents

(ethanol, methanol, acetonitrile, pyrrole) did not yield product. In many cases, only unreacted 3-methylindole or pyrrole was recovered, and little evidence of unreacted bromoacetaldehyde diethylacetal was observed. Therefore, a second synthetic route was employed where reaction of a lithiated cyclopentadienyl moiety with bromoacetaldehyde diethylacetal would produce the corresponding acetal (48) (eq. 2). These acetals can then be reacted with 3-methylindole or pyrrole to produce constrained geometry ligands.

BrCH2CH(OEt)2 + nBuLi (2) Et2O

CH(OEt)2 48

2.4.1 Synthesis of diethylacetals

Acetals modified with fluorenyl, indenyl, or cyclopentadienyl moieties were synthesized in high yields on a large scale through reaction of deprotonated fluorene,

39 indene, or cyclopentadiene with bromoacetaldehyde diethyl acetal. Compound 48 was synthesized by addition of deprotonated fluorene to a solution of bromoacetaldehyde diethylacetal in diethyl ether at 0 °C. After workup, compound 48 was isolated as a pale yellow oil that solidified upon standing for several days in 93% yield. It should be noted that the synthesis of 48 can be increased to a 40-50 g scale without decrease in percent yield. The 1H NMR spectrum of 48 (Figure 2.3) showed one set of resonances for the fluorenyl moiety with two doublets at 7.73 and 7.54 ppm and two triplets at 7.34 and 7.28 ppm for H4, H1, H3, and H2, respectively. There is one triplet resonance at 4.68 ppm for the methine CH, and another triplet resonance at 4.07 ppm for the fluorenyl CH of the five-membered ring. The diastereotopic nature of the methylene protons of the ethoxy groups results in two multiplets at 3.63 and 3.41 ppm for the ABX3 splitting system. A doublet of doublets resonance is observed at 2.20 ppm, which integrates to two protons for the methylene protons of the carbon bridge. There is also one triplet resonance at

1.12 ppm for the methyl resonances of the ethoxy groups.

CH(OEt)2 48

CH3

OCH2 fluorene CH CH2 CH, flu

Figure 2.3. 1H NMR spectrum of fluorenyl acetaldehyde diethylacetal (48)

Compound 49 was synthesized and isolated using an analogous method to 48.

Indenyl acetaldehyde diethylacetal was isolated as a light brown oil that showed distinct features in the 1H and 13C NMR spectrum for an asymmetrical structure. There was one set of indene resonances with two doublets at 7.43 and 7.35 ppm and two triplets at 7.25 and 7.19 ppm for H4, H7, H5, and H6, respectively. There were two doublets of doublets at 6.80 and 6.61 ppm for H2 and H3, respectively, of the five-membered indene ring. A triplet resonance at 4.68 ppm arose from the methine CH, and two multiplets resonances at 3.69 and 3.52 ppm corresponded to the diastereotopic methylene protons of the carbon backbone. A multiplet resonance at 3.56 ppm was observed for the CH proton of the indene ring, and two multiplet resonances at 2.22 and 1.71 ppm for the diastereotopic protons of the ethoxy groups. Furthermore, two triplet resonances were observed at 1.23

41 and 1.19 ppm for the methyl protons of the ethoxy groups, which is indicative of an asymmetric structure (Figure 2.4). The relatively simple nature of the 1H NMR spectrum indicates only one isomer was formed, where the indene five-membered ring was tethered to the alkyl chain at C1.

CH(OCH2CH3)2 49

CH3 Inde-CH

OCH OCH CH2 CH 2 2

Figure 2.4. 1H NMR spectrum of the aliphatic region of 49.

Compound 50 was synthesized according to published procedures.114,115 After thermally cracking dicyclopentadiene, a cold THF solution of cyclopentadiene was slowly added to sodium hydride in THF. The resulting pale pink solution was then added dropwise to bromoacetaldehyde diethylacetal in THF. After workup, compound 50 was isolated as a brown oil. All resonances in the 1H and 13C NMR spectra match those previously reported, and indicate the formation of the 1,2- and 1,3-isomers of 50.114

2.4.2 Synthesis of constrained geometry ligands

The formation of diindolyl- and dipyrrolyl-methanes is well documented in the literature, and these compounds are typically prepared through acid-catalyzed condensation with aldehydes, acetals, or ketones.100,113,120-122 Various syntheses have been implemented with acid catalysts such as ZrCl4, In(OTf)3, Ga(ClO4)3, HCl, H2SO4,

CF3CO2H, CuCl2, and others. Fluorenyl di(3-methylindolyl)ethane (51), abbreviated as

H3FDI, was synthesized via two different acid-catalyzed condensation methods (eq. 3).

In the first method, 48 and 3-methylindole were dissolved in methanol, and a catalytic amount of concentrated sulfuric acid was added via syringe. The brown reaction mixture was heated to 40-45 °C for 12 h. After cooling to room temperature, and proper workup, storage of the concentrated reaction solution at 30 °C resulted in the formation of a yellow precipitate. Compound 51 was isolated in 60% yield.

Method 1: H2SO4 MeOH HN + 2 H H (3) Method 2: N ZrCl4 CH(OEt)2 CH3CN N H

48 51

In the second synthetic route to 51, a solution of 48 in acetonitrile was added to a solution of 3-methylindole in acetonitrile. A solution of ZrCl4 (10 mol%) in acetonitrile was added to this mixture and stirred overnight at room temperature. After appropriate workup, compound 51 was isolated as a yellow solid in 59% yield. Both method 1 and method 2 for the synthesis of 51 result in yields around 60%. It should be noted that

43 method 1 can be scaled to yield multi-gram crops of H3FDI (51). Method 2 has not been optimized for scale-up of H3FDI, although multi-gram syntheses have been performed for

H3IDI (53) with this method. Since yields are essentially equal in both methods, method

1 is preferred for the synthesis of compound 51. This method is preferred for two reasons: 1) air- and moisture-sensitive techniques are not required, and 2) purification by column chromatography, which uses of large amounts of organic solvents, is not required.

The 1H NMR spectrum of 51 shows one set of resonances for fluorene, and one set of resonances for the indolyl moieties. Integrations of these resonances indicate the presence of two indoles per fluorene. A broad singlet resonance at 7.69 ppm for the NH protons is observed. Two doublet resonances of the indole moieties are evident at 7.66 and 7.43 ppm for H7 and H4, respectively. Two triplet resonances for the indole moieties are evident at 7.26 and 7.07 ppm for H6, and H5, respectively. For the fluorenyl moiety, two doublet resonances are observed at 7.47 and 7.21 ppm for H4 and H1, respectively, and two triplet resonances are observed at 7.19 and 7.12 ppm for H3 and H2, respectively. The specific aromatic assignments were made on the basis of gHMBC and gCOSY experiments (Figure 2.5). There is a triplet resonance at 4.75 ppm for the methine CH and another triplet resonance at 4.00 ppm for the proton of the fluorenyl five-membered ring. A doublet of doublets resonance is observed at 2.72 ppm for the methylene protons of the ligand bridge, and a singlet resonance at 2.12 ppm for the six methyl protons of the indole moieties. The appearance of one singlet resonance for the indolyl methyl groups suggests a symmetrical ligand structure.

Indo-H7 Indo-H4 Indo-H6

Flu-H4 Indo-H5 NH

Indo-H5

Indo-H6

Flu-H4 Indo-H4

Indo-H7 NH

Figure 2.5. gCOSY spectrum of the aromatic region of 51 in chloroform-d.

Crystals of 51·THF were grown from concentrated toluene/THF solution at 30

°C and analyzed by X-ray crystallography. Crystallographic data confirms the structure of 51 as proposed by NMR methods. The space group P21/n was chosen for preliminary solution of the structure. As confirmed by crystallographic and NMR data, there is one

THF molecule hydrogen bound to the nitrogen protons of the indole moieties (Figure

2.6). Bond distances for N1 O1 and N2 O1 are 2.952(2) Å and 3.055(2) Å, respectively, and are in the range for other reported hydrogen bonded molecules with indole moieties.100

Figure 2.6. ORTEP diagrams of 51. Thermal ellipsoids are drawn at the 30%

probability level. Non-nitrogen bound hydrogen atoms are omitted for

clarity.

Table 2.2. Selected bond distances and angles for compound 51·THF ______Bond distances (Å) C1 C2 1.538(3) C10 N1 1.389(2) C1 C10 1.504(3) N1 O1 2.952(2) C2 C3 1.545(3) N2 O1 3.055(2)

Bond angles (deg) C2 C1 C10 110.46(15) C1 C10 C11 130.16(17) C1 C2 C3 116.76(16) C1 C10 N1 120.60(16) C10 N1 C17 109.09(16) ______

Compound 52 (H3FDP) was synthesized by a similar route to the second synthetic method for the synthesis of 51. However, instead of reaction with only two equivalents

46 of pyrrole, the reaction was carried out with four equivalents to minimize condensation at

C2 and C5 on the same pyrrole ring (eq. 4).

ZrCl4 HN CH3CN + 4 (4) H H N

CH(OEt)2 N H

48 52

A solution of 48 in acetonitrile was added to a solution of pyrrole in acetonitrile.

A solution of ZrCl4 (10 mol%) in acetonitrile was added to this mixture, which turned brown and was stirred at room temperature overnight. After a similar workup to that of method 2 for 51, compound 52 was isolated as a light brown solid. In the 1H NMR spectrum, a single set of resonances was present for the pyrrolyl protons, and one set of resonances for the fluorenyl moiety. Integrations of these resonances were consistent with two pyrroles per fluorene. There is a broad singlet resonance at 7.63 ppm for the nitrogen protons. For the fluorenyl protons, two doublet resonances are observed at 7.74 and 7.43 ppm for H4 and H1, respectively. Two triplet resonances are observed at 7.34 and 7.26 ppm for H3 and H2, respectively. For the pyrrole resonances, a doublet of doublets resonance is observed at 6.57 ppm for H4, and two broad doublet resonances at

6.12 and 6.09 ppm are observed for H5 and H3, respectively. A triplet resonance is observed at 4.38 ppm for the methine CH, and another triplet at 3.90 ppm is evident for the proton of the fluorene five-membered ring. A doublet of doublets resonance is shown at 2.44 ppm for the two equivalent methylene protons of the carbon bridge. It should be noted that there are some minor peaks in the baseline of the 1H NMR spectrum of 52

47 even after purification (Figure 2.7). These resonances seem to suggest some minor formation of N-confused products, wherein condensation occurs at C3 of the pyrrole ring instead of C2. This type of reactivity has been demonstrated for other pyrrole-based systems.123 Attempts to separate these two products by column chromatography or crystallization were unsuccessful. Specific assignments for carbon resonances of the fluorenyl H1a and H4a and for the pyrrolyl H2 were made based on gHMQC and gHMBC experiments (Figure 2.8).

3 4 2

H H N 5 3 N 4 H

flu-H4 flu-H1 flu-H3 flu-H2 pyrr-H4 pyrr-H5 pyrr-H3

1 Figure 2.7. H NMR spectrum of the aromatic region of H3FDP (52).

Pyrr-C3 Flu-C1a Flu-C4a Pyrr-C2

CH2

Flu-CH CH

Figure 2.8. gHMBC spectrum of H3FDP (52).

Synthesis of indenyl di(3-methylindolyl)ethane (53), abbreviated as H3IDI, was carried out via the same route as for compound 51. Compound 53 was isolated as a bright yellow solid after purification by silica gel column chromatography with 20% methylene chloride in hexanes (eq. 5).

ZrCl4 CH CN HN 3 (5) + 2 H H N

CH(OEt)2 N H

49 53

The 1H and 13C NMR spectra for 53 suggested an asymmetrical structure as expected (Figure 2.10 and Figure 2.11). Integrations of the NMR resonances were consistent with two indoles per indene. In the aromatic region of the spectrum, there were two separate sets of resonances for the two chemically inequivalent indole moieties and one set of resonances for the indenyl moiety (Figure 2.10). In this instance, 2D NMR experiments were employed to assist in 1H and 13C assignments. There are two broad singlet resonances at 7.85 and 7.79 ppm for the nitrogen protons on the inequivalent indole moieties. Four doublet resonances of the indoles were observed, which all integrate to one proton each at 7.53, 7.49, 7.34, and 7.28 ppm for H7 and H4, respectively. Furthermore, four triplet resonances that integrate to one proton each are observed at 7.24, 7.16, 7.15, and 7.13 ppm for H6 and H5, respectively. The indenyl protons are observed as two doublet resonances that integrate to 1 at 7.39 and 7.23 ppm for H4 and H1, respectively. There are two triplet resonances at 7.12 and 7.09 ppm for

H3 and H2, respectively. Two doublet resonances of the indene five-membered ring are observed at 6.75 and 6.39 ppm for H2 and H3, respectively. In the 1H NMR spectrum, the methine proton appears as a doublet of doublets at 4.76 ppm since it is coupled to the two diastereotopic protons of the carbon bridge. The inequivalent methylene protons are observed as two multiplet resonances at 2.74 and 2.18 ppm, respectively. Another multiplet resonance is observed at 3.44 ppm for H1 of the indene five-membered ring.

Two singlet resonances are observed at 2.33 and 2.23 ppm for the methyl groups of the indole moieties, which is consistent with an asymmetrical structure (Figure 2.11).

Although overlapping resonances are observed in the aromatic region of the 1H NMR

50 spectrum of 53, assignments were made based on gCOSY, gHMQC, and gHMBC experiments (Figure 2.12).

3 4 3a 2 5 1 7a 6 7 8 H 3 N 3a 2 4 HN 7a 5 7 6

Figure 2.9. NMR numbering scheme for H3IDI (53).

indene, CH NH

Figure 2.10. 1H NMR spectrum of the aromatic region of 53.

CH3

CH2

CH, methine CH, indene

Figure 2.11. 1H NMR spectrum of the aliphatic region of 53.

Indo-H4 Indo-H7 Inde-H4 NH Inde-H3 Inde-H2

Inde-H2

Inde-H3

Indo-H4 Inde-H4 Indo-H7

Figure 2.12. gCOSY spectrum of the aromatic region of 53.

Compound 54 (H3IDP) was synthesized in low yield by an analogous method to that of 52. Again, four equivalents of pyrrole were used to minimize condensation at C2 and C5 of the same pyrrole ring. The 1H NMR spectrum is indicative of an asymmetrical structure, as expected with one indene moiety present. There are two broad singlet resonances at 7.84 and 7.79 ppm for the nitrogen protons. One set of indenyl resonances is observed, with two doublet resonances at 7.41 and 7.36 ppm for H7 and H4, respectively, as well as two triplet resonances at 7.25 and 7.18 ppm for H6 and H5,

52 respectively. There are two resonances for the protons on the five-membered indene ring that are observed as two doublets at 6.75 and 6.34 ppm for H2 and H3, respectively.

There are six total resonances for the two pyrrole moieties, although two of these resonances overlap, resulting in five observed multiplets. Multiplet resonances are observed at 6.68, 6.40, 6.17, 6.14, and 6.09 ppm for H5, H5b, H4/H4b, H3 and H3b, respectively. There is a doublet of doublets resonance at 4.22 ppm for H1, and three multiplet resonances at 3.38, 2.47, and 1.97 ppm for H7, H6, and H6b, respectively. It should be noted that similar scenario to compound 52, compound 54 exhibits minor resonances in the 1H NMR spectrum indicative of the formation of N-confused products.

Attempts to separate these products were unsuccessful.

Attempts to synthesize di(3-methylindolyl)- or dipyrrolyl- ligands with cyclopentadienyl acetaldehyde diethylacetal (50) via acid-catalyzed condensation methods were unsuccessful. Reactions were performed with several acid catalysts, and under several different reaction conditions. In reactions with 3-methylindole, protic acids such as sulfuric acid and hydrochloric acid were used with methanol or ethanol as the solvent. Lewis acid catalysts such as zirconium tetrachloride and indium chloride were used with acetonitrile or methylene chloride as the solvent. Room temperature reactions to reflux temperature reactions over several hours to several days were also performed.

In most cases, a majority of unreacted 3-methylindole was recovered, although presence of 50 was not detected by 1H NMR. For reactions of 50 with pyrrole, trifluoroacetic acid was used with ethanol, methanol, or pyrrole as the solvent. Zirconium chloride was used as a Lewis acid catalyst with acetonitrile or methylene chloride as the solvent. Reactions were performed at various temperatures and for various periods of time ranging from

53 several hours to several days. In all cases, at least a two fold excess of pyrrole was used to minimize condensation at multiple locations of the same pyrrole moiety. Each attempt resulted in either no reaction or a mixture of unidentified products that did not give the expected 1H NMR spectra for product formation even after purification. In most cases, a majority of unreacted pyrrole was present, and presence of 50 was not detected by 1H

NMR. It is postulated that the relative reactivity of the cyclopentadienyl protons of 50 could play a role in hindering product formation. In fact, condensation at the cyclopentadienyl protons has been reported to produce some bisferrocene derivatives via acid-catalyzed condensation.124

2.5 Conclusions

The synthesis and characterization of a new series of acetals and di(3- methylindolyl)ethane and dipyrrolylethane constrained geometry ligands is reported.

Synthesis of fluorenyl (48), indenyl (49), and cyclopentadienyl (50) acetals is straightforward and gives high yields. The formation of di(3-methylindolyl)ethanes via acid-catalyzed condensation results in the formation of two new constrained geometry ligands, 51 and 53, in good yield. Synthesis of dipyrrolylethanes via acid-catalyzed condensation is less straightforward, and works in moderate to low yields resulting in the formation of 52 and 54. This new set of constrained geometry ligands could be very useful in the formation of constrained geometry complexes with various transition metals.

Chapter Three

Constrained Geometry and Related Complexes of Group 4 and 5 Metals

3.1 Introduction

Constrained geometry complexess such as 1 and 2 were first introduced in the open literature by Shapiro (1),3 and Okuda (2),4 and in patents by Canich and coworkers at Exxon,56 and Stevens and coworkers at Dow Chemical.2 Early constrained geometry catalysts focused on transition metals like scandium or titanium, and typically featured ligands with one pendant amido donor and one tetramethylated cyclopentadienyl moiety.

CGCs have been examined for their utility in the polymerization and copolymerization of alkenes, where the more constrained angle that is imposed by the tethered ligand results in a more accessible metal center compared to those of ansa-metallocenes. This generates a more open coordination site for substrate binding.

H Si Sc Sc Si Si Ti Cl H Cl N PMe3 PMe3 N N tBu tBu tBu 1 2

Continued research and development of CGCs has culminated in the formation of numerous complexes of early, mid, and late transition metals, though a vast majority of

55 current constrained geometry complexes consists of group 4 transition metals, particularly titanium and zirconium. Group 4 CGCs are useful in polymerizations and copolymerizations since they are typically formed with dianionic ligands, forming cationic species with one alkyl group upon alkide abstraction from the metal center. This environment, as well as any steric constraints imposed by the symmetry of the ligand, can allow for control over polymer tacticity. Control can be further tuned by altering the stereochemistry of the ligand and limiting substrate coordination to only one orientation.

Titanium and zirconium CGCs with dianionic ligands have certainly been prominent as polymerization catalysts. Only a select few group 4 CGCs have been prepared with trianionic ligands (20, 21, 57).41,75,104,125 It would not be anticipated that complexes of group 4 metals with trianionic ligands would be suitable for alkene polymerizations since alkide abstraction would result in a cationic complex with no alkyl group left for insertion of the coordinating alkene. However, Cano and coworkers have shown that complex 20 is active in the polymerization of ethylene in the presence of

75 B(C6F5)3, although the mechanism is unknown. CGCs featuring trianionic ligands may be more useful as alkene polymerization catalyst when a group 5 metal is used. Alkide abstraction from a group 5 complex of this type should result in a cationic complex with one alkyl group available for chain propagation, mirroring traditional group 4 complexes with dianionic ligands. This approach has not yet been investigated.

Me2Si Me2Si SiMe2 Me Si 2 N N Zr Ti Zr N N tBu t t N N CH3 Bu Bu NMe2 Bz tBu 20 21 57

Aside from constrained geometry complexes of group 4 transition metals, several other transition metal CGCs have been formed, although their application in alkene polymerization or other catalytic processes has not been fully explored. Reports on constrained geometry complexes of group 5 metals have been limited.60-64 Known examples are focused mainly on vanadium complexes (e.g. 16). Constrained geometry complexes of niobium (18a) or tantalum (18b) are essentially non-existent. Furthermore, although CGCs with transition metals of groups 6 to 9 are known, reports of these complexes are also limited.5 Indeed, group 4 CGCs with dianionic ligands are the most explored complexes of constrained geometry catalysts.

NMe Me2Si M 2 V Cl N NMe2 Cl NMe2 N Ph iPr

16 18a M = Nb 18b M = Ta

A vast majority of constrained geometry complexes feature monoanionic pendant amido donors.1,5 The use of amido donors in early transition metal CGCs results in additional N M donation, which helps stablilize early metal complexes. The basicity of amido donors is considerably high, and typically more than two-electron donation is suggested by a significantly shortened N M bond distance and trigonal planar geometry of the amido nitrogen as observed by X-ray structural analysis.126 While the increased donation to the metal center presumably increases the stability of the complex, electrophilicity of the metal center is most likely decreased. A contrasting situation is observed in pyrrolyl-based CGCs. An elongated N M bond is observed in comparison to related amido complexes, which suggests reduced electron donation.41 Therefore, the use

57 of nitrogen heterocycles such as 3-methylindole as a pendant donor could result in the formation of stable metal complexes that exhibit a reduced N M donation.113 This should create a more electrophilic metal center and could result in a highly active alkene polymerization catalyst upon coordination to an early transition metal.

For these reasons, we set out to develop constrained geometry complexes of group 4 and 5 transition metals with trianionic indolyl- and pyrrolyl-based ligands. It was envisioned that these ligands should form stable, 12- to 14-electron metal complexes upon coordination to group 4 and 5 transition metals. Alkyl complexes of this type could prove active in the polymerization and copolymerization of alkenes. Furthermore, group

5 imido complexes can be formed with this framework, which could be useful in catalytic applications such as alkene or alkyne hydroamination. These types of complexes should be structurally analogous to those prepared by Otero et al.59,74

Transition metal-imido complexes have been reported previously, and group 4 imido complexes have been of particular interest for research groups including

Mountford87-89 and Arnold.93-95 Although the chemistry of mid to late transition metal imido complexes has been explored for a considerable number of years, early metal- imido complexes are still in their infancy.79 Difficulties in preparing group 4 imido complexes arises around the relative instability of the metal-imido moiety due to an increase in the imido bond polarity from the mid to early transition metals.127 Recent advancements in metal-imido research have resulted in the preparation of stable group 4 imido complexes, particularly with titanium.83,84 In fact, a tridentate diamido pyridyl ligand has been used for the relatively straightforward synthesis of a series of titanium- imido complexes (31).87 Preparation of analogous zirconium-imido complexes is not

58 conducted as easily, and has essentially only been performed with bulky arylimido moieties.

N N Ti NtBu Me Si N 3 py Me3Si 31

A closely related set of di(3-methylindolyl)methane ligands has been previously explored by the Mason group in the formation of group 4 diamido and dicyclopentadienyl complexes.98,101,102 Using this framework, a series of titanium-imido complexes were explored. These complexes feature two monoanionic 3-methylindolyl moieties and one neutral donor such as a pyridyl, methoxyphenyl, or N-methylimidazolyl moiety. These complexes are structurally analogous to those reported by Mountford et al., and are believed to be stable, 10- to 12-electron complexes that could be useful in the hydroamination or polymerization of alkenes.

In this chapter, the synthesis and characterization of group 4 and 5 constrained geometry complexes featuring 3-methylindolylmethanes is discussed. Specifically, three new amido complexes of titanium and zirconium are reported: the bidentate complexes

(HFDI)Zr(NEt2)2(THF) (58) and (HFDI)Ti(NEt2)2 (59), as well as a constrained geometry complex (IDI)Zr(NEt2) (60). The synthesis and characterization of two other constrained geometry complexes (FDI)Zr(CH3) (61) and (FDI)Ti(CH3) (62) are also reported. Two group 5 constrained geometry imido complexes were reported,

(IDI)Nb(NtBu)(py) (63) and (IDI)Nb(NPh) (64). This series of complexes represents the first report of group 4 and 5 constrained geometry complexes featuring trianionic indolyl-

59 based ligands. Also reported in this chapter are the syntheses and characterization of three new titanium-imido complexes of di(3-methylindolyl)methanes. Specifically, the transition metal-imido complexes (tBuN)Ti{(2-pyridyl)di(3-methylindolyl)methane}

(65), (tBuN)Ti{(2-methoxyphenyl)di(3-methylindolyl)methane} (66), and (tBuN)Ti{(N- methylimidazole)di(3-methylindolyl)methane} (67) were prepared. These complexes represent the initial investigation of group 4 imido complexes using this ligand framework.

O N N N(CH2CH3)2

Zr N(CH2CH3)2 Ti

N N N(CH2CH3)2 N(CH2CH3)2

58 59

H Zr H N M NEt2 N CH N 3 N

60 M = Zr (61), Ti (62)

H Nb H Nb t N N Bu N NPh N N N

63 64

N H H H N O CH3 N t t t N Ti N Bu N Ti N Bu N Ti N Bu N N N N N N

65 66 67

3.2 Experimental

General Procedures

All air- and moisture-sensitive reactions were performed in an inert atmosphere of purified nitrogen using standard inert atmosphere techniques and an Innovative

Technologies dry box. Toluene was distilled from sodium, hexanes and methylene chloride were distilled from calcium hydride, and diethyl ether and tetrahydrofuran were distilled from sodium benzophenone ketyl prior to use. Methyllithium (1.6 M in diethyl ether) and n-butyllithium (1.6 M in hexanes) were purchased from Aldrich and used as received. Zirconium(IV) chloride and titanium(IV) chloride were purchased from

Aldrich and used without further purification. The compounds ZrCl4(THF)2,

128 129,130 t 131 132 TiCl4(THF)2, Zr(NEt2)4, Ti(NEt2)4, ( BuN)NbCl3(py)2, (PhN)NbCl3(dme),

61 t 133,134 102 ( BuN)TiCl2(py)3, di(3-methylindolyl)-2-pyridylmethane, 2-methoxyphenyldi(3- methylindolyl)methane,100 and di(3-methylindolyl)-N-methylimidazolylmethane103 were prepared according to published procedures. Chloroform-d and benzene-d6 were dried by storage over activated molecular sieves. Solution NMR spectra were recorded on a

Varian AS-600 spectrometer. Chemical shifts are reported relative to TMS. 1H and 13C

NMR assignments were aided by 2D-COSY and 2D-HMQC and 2D-HMBC experiments. For a numbering scheme of indole, fluorene, and indene, refer to Figure

2.2.

Synthesis of (HFDI)Zr(NEt2)2(OC4H8) (58)

Fluorenyl di(3-methylindolyl)ethane (51) (0.300 g, 0.663 mmol) was dissolved in

20 mL of toluene. A solution of Zr(NEt2)4 (0.252 g, 0.663 mmol) in 10 mL of toluene was added via cannula. The resulting brown reaction mixture was refluxed for 2 h, then cooled to room temperature and filtered. Volatiles were removed in vacuo from the filtrate, leaving a brown residue. The residue was dissolved in a minimal amount of hot

THF and placed in a freezer ( 30 °C) overnight. Pale yellow crystals were isolated by decantation and dried in vacuo. X-ray quality crystals were obtained by recrystallization

1 from hot toluene/THF. Yield: 0.402 g, 0.530 mmol, 80%. H NMR (benzene-d6, 600

3 3 MHz): 7.72 (d, JHH = 7.8 Hz, 2H, indo-H7), 7.62 (d, JHH = 7.8 Hz, 2H, indo-H4), 7.47

3 3 (d, broad, JHH = 7.8 Hz, 2H, flu-H4), 7.36 (d, broad, 2H, flu-H1), 7.33 (t, JHH = 7.8 Hz,

3 3 2H, indo-H6), 7.32 (t, JHH = 7.8 Hz, 2H, indo-H5), 7.19 (t, JHH = 7.8 Hz, 2H, flu-H3),

3 3 3 7.06 (t, JHH = 7.8 Hz, 2H, flu-H2), 5.04 (t, JHH = 7.2 Hz, 1H, C, 4.28 (t, JHH = 7.2 Hz,

1H, flu-CH), 3.66 (m, broad, 4H, THF), 3.46 (q, 2H, NCH2CH3), 3.24 (q, broad, 4H,

NCH2CH3), 2.85 (dd, 2H, CH2), 2.29 (s, 6H, CH3), 1.24 (m, broad, 4H, THF), 0.86 (t,

3 3 13 1 JHH = 6.6 Hz, 6H, NCH2CH3), 0.55 (t, JHH = 6.6 Hz, 6H, NCH2CH3). C{ H} NMR

(benzene-d6, 150.8 MHz): 148.1 (s, flu-C1a), 148.0 (s, flu-C4a), 144.7 (s, indo-C7a),

142.0 (s, indo-C3a), 132.5 (s, indo-C2), 127.9 (s, flu-C3), 127.5 (s, flu-C2), 125.7 (s, flu-

C4), 120.5 (s, indo-C4), 120.0 (s, indo-C5), 118.9 (s, indo-C6), 118.8 (s, indo-C7), 114.7

(s, flu-C1), 106.7 (s, indo-C3), 72.5 (s, THF), 48.8 (s, flu-CH), 45.7 (s, CH2), 42.1 (s, broad, NCH2CH3), 40.3 (s, NCH2CH3), 35.8 (s, CH), 26.1 (s, THF), 15.0 (s, NCH2CH3),

13.7 (s, NCH2CH3), 9.6 (s, CH3).

Synthesis of (HFDI)Ti(NEt2)2 (59)

Fluorenyl di(3-methylindolyl)ethane (51) (0.252 g, 0.557 mmol) was dissolved in

15 mL of toluene. A solution of Ti(NEt2)4 (0.270 g, 0.803 mmol) in 5 mL of toluene was added via cannula. This brown reaction mixture was refluxed for three days, then cooled to room temperature and filtered. Volatiles were removed in vacuo from the filtrate, leaving a brown residue. The residue was dissolved in a minimal amount of hot toluene and placed in a freezer ( 30 °C) overnight. Pale yellow crystals of free ligand formed, and the supernatant was decantated and dried in vacuo. The product was isolated from the supernatant as a brown/orange solid. Yield: 0.165 g, 0.256 mmol, 46%. 1H NMR

3 3 (benzene-d6, 600 MHz): 7.60 (d, JHH = 7.2 Hz, 2H, indo-H7), 7.50 (d, JHH = 6.6 Hz,

3 3 2H, indo-H4), 7.46 (d, broad, JHH = 7.8 Hz, 2H, flu-H4), 7.36 (d, JHH = 7.2 Hz, 2H, flu-

3 3 H1), 7.28 (t, JHH = 7.2 Hz, 2H, indo-H6), 7.25 (t, JHH = 7.2 Hz, 2H, indo-H5), 7.17 (t,

3 3 3 JHH = 7.2 Hz, 2H, flu-H3), 7.04 (t, JHH = 7.2 Hz, 2H, flu-H2), 4.88 (t, JHH = 7.2 Hz,

3 1H, C, 4.04 (t, JHH = 7.2 Hz, 1H, flu-CH), 3.68 (q, 4H, NCH2CH3), 3.42 (q, 2H,

3 NCH2CH3), 2.84 (dd, 2H, CH2), 2.11 (s, 6H, CH3), 1.10 (t, JHH = 6.6 Hz, 4H,

3 13 1 NCH2CH3), 0.68 (t, JHH = 6.6 Hz, 6H, NCH2CH3). C{ H} NMR (benzene-d6, 150.8

MHz): 147.49 (s, flu-C1a), 147.34 (s, flu-C4a), 143.41 (s, indo-C7a), 141.56 (s, indo-

C3a), 130.56 (s, indo-C2), 127.32 (s, flu-C3), 126.93 (s, flu-C2), 124.43 (s, flu-C1),

121.54 (s, indo-C6), 120.58 (s, indo-C5), 120.08 (s, indo-C7), 118.30 (s, indo-C4),

115.27 (s, flu-C4), 107.82 (s, indo-C3), 47.61 (s, NCH2CH3), 47.26 (s, flu-CH), 46.79 (s,

NCH2CH3), 43.34 (s, CH2), 34.75 (s, CH), 15.33 (s, NCH2CH3), 15.13 (s, NCH2CH3),

9.11 (s, CH3).

Synthesis of (IDI)Zr(NEt2) (60)

Indenyl di(3-methylindolyl)ethane (53) (0.150 g, 0.381 mmol) was dissolved in

15 mL of toluene. A solution of Zr(NEt2)4 (0.141 g, 0.381 mmol) in 10 mL of toluene was added via cannula. The resulting brown reaction mixture was heated for 2 h, then cooled to room temperature and filtered. Volatiles were removed in vacuo, leaving a brown residue. The residue was dissolved in a minimal amount of hot toluene, and placed in a freezer ( 30 °C) overnight. Pale yellow crystals were isolated by decantation and dried in vacuo. Crystals suitable for X-ray analysis were obtained by

1 recrystallization from hot toluene. Yield: 0.110 g, 0.205 mmol, 55%. H NMR (CDCl3,

3 3 600 MHz): 7.85 (d, JHH = 7.8 Hz, 1H, indo-H7), 7.44 (m, 1H, inde-H4), 7.40 (d, JHH =

7.8 Hz, 1H, indo-H4), 7.07 (m, 2H, indo-H4, indo-H6), 7.02 (m, 2H, indo-H5, inde-H5),

3 3 3 6.93 (t, JHH = 7.2 Hz, 1H, indo-H6), 6.85 (d, JHH = 3.6 Hz, 1H, inde-H2), 6.81 (t, JHH =

3 3 7.2 Hz, 1H, inde-H6), 6.58 (t, JHH = 7.2 Hz, 1H, indo-H5), 6.46 (d, JHH = 8.4 Hz, 1H,

3 3 indo-H7), 6.23 (d, JHH = 7.8 Hz, 1H, inde-H7), 6.13 (d, JHH = 3.6 Hz, 1H, inde-H3),

2 3 5.35 (dd, 1H, CH), 3.90 (m, 4H, NCH2CH3), 3.58 (dd, JHH = 13.2 Hz, JHH = 3.6 Hz, 1H,

2 3 CH2), 3.37 (dd, JHH = 13.2 Hz, JHH = 3.6 Hz, 1H, CH2), 2.45 (s, 3H, CH3), 2.44 (s, 3H,

3 13 1 CH3), 1.24 (t, JHH = 6.6 Hz, 6H, NCH2CH3). C{ H} NMR (CDCl3, 150.8 MHz):

145.81 (s, indo-C7a), 144.93 (s, indo-C7a), 142.21 (s, inde-C3a), 141.98 (s, inde-C1a),

137.86 (s, inde-C3a), 131.00 (s, indo-C3a), 130.58 (s, indo-C3a), 126.78 (s, inde-C7a),

124.71 (s, indo-C6), 124.27 (s, indo-C5), 122.10 (s, indo-C7), 121.77 (s, inde-C3),

121.73 (s, indo-C7), 120.57 (s, indo-C5), 120.18 (s, inde-C6), 119.25 (s, inde-C5), 118.44

(s, indo-C6), 117.92 (s, inde-C4), 117.79 (s, indo-C4), 114.29 (s, indo-C4), 113.56 (s, inde-C7), 99.65 (s, inde-C2), 40.67 (s, NCH2CH3), 36.42 (s, CH), 34.82 (s, inde-C1),

15.85 (s, NCH2CH3), 9.14 (s, CH3), 9.06 (s, CH3).

Synthesis of (FDI)Zr(CH3) (61)

Fluorenyl di(3-methylindolyl)ethane (51) (0.500 g, 1.10 mmol) was dissolved in

15 mL of diethyl ether and cooled to 78 °C. A solution of MeLi in diethyl ether (2.8 mL, 1.6 M, 4.4 mmol) was added dropwise via syringe. Upon warming to room temperature, the red solution was stirred for 12 h. The reaction mixture was cooled to

78 °C, and ZrCl4(THF)2 (0.420 g, 1.10 mmol) was added as a solid. The reaction mixture was warmed to room temperature and stirred for 3 h. Volatiles were removed in vacuo, and 20 mL of methylene chloride were added. The cloudy orange reaction mixture was filtered through Celite, and volatiles were removed in vacuo, leaving an

1 orange/red solid. Yield: 0.424 g, 0.605 mmol, 55%. H NMR (CDCl3, 600 MHz):

3 3 3 7.97 (d, JHH = 8.4 Hz, 2H, flu-H4), 7.44 (d, JHH = 7.8 Hz, 2H, indo-H4), 7.27 (d, JHH =

3 3 8.4 Hz, 2H, flu-H1) 7.18 (t, JHH = 7.2 Hz, 2H, flu-H3), 6.97 (t, JHH = 7.2 Hz, 2H, indo-

3 3 H5), 6.86 (t, JHH = 7.2 Hz, 2H, indo-H6), 6.65 (t, JHH = 7.2 Hz, 2H, flu-H2), 6.27 (d,

3 3 3 JHH = 8.4 Hz, 2H, indo-H7), 5.20 (t, JHH = 6.6 Hz, 1H, CH), 3.64 (d, JHH = 3.6 Hz, 1H,

CH2), 3.42 (m, br, 4H, THF), 3.10 (q, br, 4H, Et2O), 2.55 (s, 2H, CH3), 1.55 (m, br, 4H,

13 1 THF), 1.16 (t, br, 6H, Et2O), 0.42 (s, 3H, Zr CH3). C{ H} NMR (CDCl3, 150.8

MHz): 145.11 (s, indo-C3a), 132.46 (s, indo-C7a), 128.18 (s, flu-C1a), 127.04 (s, flu-C2),

124.39 (s, flu-C4), 121.59 (s, flu-C3), 119.68 (s, indo-C7), 119.58 (s, flu-C4a), 119.21 (s, indo-C6), 117.91 (s, indo-C5), 116.68 (s, indo-C4), 116.43 (s, flu-C1), 105.37 (s, indo-

C2), 93.77 (s, indo-C3), 89.26 (s, flu-CH), 68.00 (s, THF), 65.82 (s, Et2O), 50.75 (s,

Zr CH3), 38.02 (s, CH), 34.39 (s, CH2), 25.13 (s, THF), 15.20 (s, Et2O), 15.13 (s, C16),

9.48 (s, CH3).

Synthesis of (FDI)Ti(CH3) (62)

Fluorenyl di(3-methylindolyl)ethane (51) (0.200 g, 0.440 mmol) was dissolved in

15 mL of diethyl ether and cooled to 78 °C. A solution of MeLi in diethyl ether (1.1 mL, 1.6 M, 1.8 mmol) was added dropwise via syringe. Upon warming to room temperature, the red solution was stirred for 12 h. The reaction mixture was cooled to

78 °C, and TiCl4(THF)2 (0.150 g, 0.440 mmol) was added as a solid. The reaction mixture was warmed to room temperature and stirred for 3 h. The reaction mixture was filtered over Celite, and volatiles were removed in vacuo from the filtrate, resulting in a

1 brown residue. Yield: 0.082 g, 0.16 mmol, 36%. H NMR (CDCl3, 400 MHz): 8.23

3 3 3 (d, JHH = 8.8 Hz, 2H, flu-H4), 7.27 (d, JHH = 8.0 Hz, 2H, indo-H4), 7.17 (t, JHH = 7.2

3 3 Hz, 2H, flu-H3), 6.92 (t, JHH = 7.2 Hz, 2H, indo-H5), 6.84 (t, JHH = 7.2 Hz, 2H, indo-

3 3 3 H6), 6.78 (t, JHH = 7.2 Hz, 2H, flu-H2), 6.67 (d, JHH = 8.8 Hz, 2H, flu-H1), 6.27 (d, JHH

3 3 = 8.0 Hz, 2H, indo-H7), 5.26 (t, JHH = 6.6 Hz, 1H, CH), 3.75 (d, JHH = 3.6 Hz, 2H,

CH2), 3.48 (m, br, 4H, THF), 3.46 (q, 4H, Et2O), 2.44 (s, 6H, indole CH3), 1.69 (m, br,

3 4H, THF), 1.19 (t, JHH = 7.2 Hz, 6H, Et2O), 0.30 (s, 3H, Ti CH3).

Synthesis of (tBuN)Nb(IDI)(py) (63)

Indenyl di(3-methylindolyl)ethane (53) (0.300 g, 0.745 mmol) was dissolved in

25 mL of diethyl ether and cooled to 78 °C. A solution of MeLi in diethyl ether (1.4 mL, 1.6 M, 2.2 mmol) was added dropwise via syringe. The cloudy orange/red mixture was warmed to room temperature and stirred for 12 h. This mixture was again cooled to

78 °C and added in portions via cannula to a cooled ( 78 °C) solution of t ( BuN)NbCl3(py)2 (0.320 g, 0.745 mmol) in 10 mL of toluene. The resulting purple reaction mixture was warmed to room temperature and stirred for 12 h. Volatiles were removed in vacuo, and 25 mL of methylene chloride were added. This cloudy purple reaction mixture was filtered through Celite, and volatiles were removed in vacuo from

1 the filtrate, leaving a purple solid. Yield: 0.375 g, 0.596 mmol, 80%. H NMR (CDCl3,

3 3 600 MHz): 7.90 (d, JHH = 7.8 Hz, 1H, indo-H4), 7.58 (d, JHH = 7.8 Hz, 1H, inde-H4),

3 3 3 7.38 (d, JHH = 7.2 Hz, 1H, indo-H4) 7.32 (d, JHH = 7.2 Hz, 1H, indo-H7), 7.26 (t, JHH =

3 3 7.8 Hz, 1H, indo-H5), 7.16 (d, JHH = 7.2 Hz, 1H, indo-H5), 7.12 (t, JHH = 7.8 Hz, 1H,

3 3 inde-H5), 7.08 (t, JHH = 7.8 Hz, 1H, indo-H6), 6.98 (d, JHH = 3.0 Hz, 1H, inde-H2), 6.96

3 3 3 (t, JHH = 7.8 Hz, 1H, indo-H6), 6.89 (t, JHH = 7.8 Hz, 1H, inde-H6), 6.67 (d, JHH = 7.8

3 Hz, 1H, inde-H7), 6.52 (m, br, 1H, indo-H7), 6.03 (d, JHH = 7.8 Hz, 1H, inde-H3), 5.32

2 3 2 (dd, 1H, CH), 3.48 (dd, JHH = 13.2 Hz, JHH = 3.6 Hz, 1H, CH2), 3.20 (dd, JHH = 13.2

3 Hz, JHH = 3.6 Hz, 1H, CH2), 2.44 (s, 3H, CH3), 2.41 (s, 3H, CH3), 1.53 (s, 9H,

13 1 N C(CH3)3). C{ H} NMR (CDCl3, 150.8 MHz): 149.59 (s, br, py), 145.45 (s, indo-

C7a), 144.77 (s, indo-C7a), 143.02 (s, inde-C3a), 141.56 (s, inde-C7a), 136.48 (s, br, py),

130.80 (s, inde-C1), 130.22 (s, indo-C3a), 129.41 (s, indo-C3a), 125.85 (s, indo-C7),

124.36 (s, indo-C4), 123.86 (s, indo-C5), 123.82 (s, py), 121.64 (s, inde-C6), 121.16 (s, indo-C6), 120.66 (s, inde-C3), 120.60 (s, indo-C5), 120.23 (s, indo-C6), 119.50 (s, inde-

C5), 118.37 (s, indo-C2), 117.48 (s, indo-C7), 117.18 (s, indo-C4), 115.63 (s, inde-C4),

115.13 (s, inde-C7), 111.28 (s, indo-C2), 109.35 (s, indo-C3), 109.26 (s, indo-C3), 90.44

(s, inde-C2), 38.23 (s, CH), 33.64 (s, CH2), 33.27 (s, N C(CH3)3), 32.84 (s, N C(CH3)3),

9.32 (s, CH3), 9.21 (s, CH3).

Synthesis of (PhN)Nb(IDI) (64)

Indenyl di(3-methylindolyl)ethane (53) (0.200 g, 0.497 mmol) was dissolved in

15 mL of diethyl ether and cooled to 78 °C. A solution of MeLi in diethyl ether (0.90 mL, 1.6 M, 1.5 mmol) was added dropwise via syringe. The cloudy orange/red reaction mixture was warmed to room temperature and stirred for 12 h. This mixture was again cooled to 78 °C, and added in portions via cannula to a cooled ( 78 °C) solution of

(PhN)NbCl3(dme) (0.230 g, 0.497 mmol) in 15 mL of toluene. The resulting dark red reaction mixture was warmed to room temperature and stirred for 12 h. The resulting cloudy dark red reaction mixture was filtered through Celite, and volatiles were removed

1 in vacuo from the filtrate, leaving a dark red solid. H NMR (CDCl3, 600 MHz): 7.78

3 3 (d, JHH = 8.4 Hz, 1H, indo-H7), 7.52 (m, br, 2H, indo-H4), 7.38 (t, JHH = 7.2 Hz, 2H, indo-H6, inde-H5) 7.33 (m, br, 3H, indo-H6, inde-H6, aryl-H1), 7.27 (m, br, 3H, indo-

H7, inde-H4, aryl-H1), 7.19 (m, br, 1H, inde-H7), 7.16 (m, br, 1H, indo-H5), 7.11 (m, br,

3 1H, indo-H5), 7.03 (d, JHH = 3.6 Hz, 1H, inde-H2), 6.98 (m, 1H, aryl-H2), 6.88 (m, 1H,

3 aryl-H3), 6.59 (m, 1H, aryl-H2), 6.16 (d, JHH = 3.6 Hz, 1H, inde-H3), 5.32 (dd, 1H, CH),

3.56 (dd, 1H, CH2), 3.30 (dd, 1H CH2), 2.47 (s, 3H, CH3), 2.45 (s, 3H, CH3).

Synthesis of (tBuN)Ti((2-pyridyl)di(3-methylindolyl)methane) (65)

In a 50 mL Schlenk flask, 2-pyridyl-di(3-methylindolyl)methane (0.14 g, 0.40 mmol) was dissolved in 15 mL of toluene. A solution of nBuLi in hexanes (0.50 mL,

0.80 mmol, 1.6 M) was added via syringe creating a red-brown solution. A solution of t ( BuN)TiCl2(py)3 (0.17 g, 0.40 mmol) in 10 mL of toluene was added via cannula. This dark red reaction mixture was stirred at room temperature overnight. This mixture was filtered through Celite, and volatiles were removed in vacuo and dried for 2 h, leaving a dark red residue. The residue was dissolved in a minimal amount of hot toluene, and placed in a freezer ( 30 °C) overnight. A red microcrystalline solid was isolated in

1 several crops and dried in vacuo. Yield: 0.212 g, 0.248 mmol, 62%. H NMR (CDCl3,

600 MHz): 8.56 (s, br, 2H, py H1), 8.54 (s, 1H, py H3), 7.75 (s, br, 2H, py H2), 7.48

3 3 3 (t, JHH = 7.2 Hz, 1H, H9), 7.39 (d, JHH = 7.8 Hz, 1H, H11), 7.35 (d, JHH = 7.8 Hz, 2H,

3 3 3 H7), 7.28 (d, JHH = 7.8 Hz, 1H, H8), 7.24 (t, JHH = 7.2 Hz, 1H, H10), 7.03 (d, JHH = 7.8

3 3 Hz, 2H, H4), 6.81 (t, JHH = 7.2 Hz, 2H, H6), 6.63 (t, JHH = 7.2 Hz, 2H, H5), 6.09 (s, 1H,

13 1 H1), 2.55 (s, 6H, indole CH3), 1.17 (s, 9H, N C(CH3)3) C{ H} NMR (CDCl3, 150.8

MHz): 163.15 (s, pyr-ipso), 152.77 (s, pyr C1), 144.98 (s, C7a), 143.46 (s, C3a),

138.29 (s, pyr C3), 138.29 (s, C9), 130.15 (s, C2), 124.36 (s, pyr C2), 121.42 (s, C11),

120.53 (s, C10), 117.58 (s, C5), 116.65 (s, C4), 116.47 (s, C6), 116.31 (s, C7), 110.71 (s,

C8), 102.73 (s, C3), 45.65 (s, C1), 32.62 (s, =N C(CH3)3), 31.97 (s, N C(CH3)3), 9.30 (s, indole CH3).

Synthesis of (tBuN)Ti((2-methoxyphenyl)di(3-methylindolyl)methane) (66)

In a 2-neck flask fitted with a reflux condenser and gas inlet, 2-methoxyphenyldi(3-methylindolyl)methane (0.21 g, 0.56 mmol) was placed and dissolved in 15 mL of toluene. A solution of nBuLi in hexanes (0.70 mL, 1.1 mmol, 1.6 M) was added via

t syringe, creating a red-brown solution. To this was added a solution of ( BuN)TiCl2(py)3

(0.24 g, 0.56 mmol) in 10 mL of toluene via cannula. The resulting black reaction mixture was refluxed for 12 h. This mixture was filtered through Celite, and the filtrate was concentrated in vacuo and placed on a bench top overnight. Yellow microcrystals were isolated by decantation, washed with cold toluene and dried in vacuo. Yield: 0.118

1 g, 0.252 mmol, 45%. H NMR (CDCl3, 600 MHz): 8.23 (s, br, 2H, py H1), 8.10 (s, br,

3 2H, py-H2), 7.76 (s, br, 1H, py-H3), 7.59 (t, JHH = 7.2 Hz, 2H, indo-H6), 7.42 (m, br,

3 2H, indo-H7), 7.19 (t, JHH = 7.8 Hz, 1H, aryl-H4), 7.12 (m, br, 1H, aryl-H5), 7.11 (m, br,

3 2H, indo-H4), 7.04 (m, br, 2H, indo-H6), 6.93 (t, JHH = 7.8 Hz, 1H, aryl-H3), 6.84 (m,

3 br, indo-H5), 6.80 (d, JHH = 7.8 Hz, 1H, aryl-H2), 6.01 (s, 1H, CH), 3.07 (s, OCH3), 2.48

(s, br, 6H, indole CH3), 1.17 (s, 9H, N C(CH3)3).

Synthesis of (tBuN)Ti((N-methylimidazolyl)di(3-methylindolyl)methane) (67)

In a Schlenk flask, N-methylimidazolyl-di(3-methylindolyl)methane (0.14 g, 0.40 mmol) was dissolved in 15 mL of toluene. A solution of nBuLi in hexanes (0.50 mL,

0.81 mmol, 1.6 M) was added via syringe, creating a cloudy red-orange mixture. A

t solution of ( BuN)TiCl2(py)3 (0.17 g, 0.40 mmol) in 10 mL of toluene was added via cannula. The resulting red-brown reaction mixture was stirred at room temperature for

12 h. The mixture was filtered through Celite, and volatiles were removed in vacuo, leaving a red-brown residue. The residue was dissolved in a minimal volume of hot toluene, and stored on the bench top overnight. Orange needle-like microcrystals were isolated by decantation, washed with cold toluene and dried in vacuo. Yield: 0.056 g,

1 0.10 mmol, 25%. H NMR (CDCl3, 600 MHz): 8.41 (s, br, 3H, py H1, py H3), 7.68

3 3 (s, br, 2H, py H2), 7.62 (d, JHH = 7.8 Hz, 2H, indo-H7), 7.42 (d, JHH = 7.8 Hz, 2H,

3 3 indo-H4), 6.92 (t, JHH = 7.2 Hz, 2H, indo-H6), 6.85 (t, JHH = 7.2 Hz, 2H, indo-H5), 6.78

3 3 (d, JHH = 7.6 Hz, 1H, imid-H5), 6.71 (d, JHH = 7.6 Hz, 1H, imid-H4), 6.18 (s, 1H, CH),

3.48 (s, 3H, imid CH3), 2.45 (s, 6H, indole-CH3), 1.14 (s, 9H, N C(CH3)3).

3.3 X-ray Crystallography

Crystals of 58 were grown from a concentrated THF solution stored at 30 °C.

Crystals of 60 were grown from a concentrated toluene solution stored at 30 °C. The X- ray diffraction data were collected on a Siemens three-circle platform diffractometer equipped with a 4K CCD detector. The frame data were collected with the SMART

5.625116 software using Mo K radiation ( = 0.71073 Å). Cell constants were determined with SAINT 6.22117 from the complete data set. A complete hemisphere of data was collected using (0.3°) scans with a run time of 30 s/frame at different angles. A total of 1415 frames were collected for each dataset. An additional 50 frames, identical to the first 50, were collected to determine crystal decay. The frames were integrated using the SAINT 6.22 software, and the data were corrected for absorption and

71 decay using the SADABS118 program. The structure was solved by direct methods and refined by least-squares methods on F2, using the SHELXTL program suite.119 Details of data collection and refinement are provided in Table 3.1. Selected bond distances and angles for 58 and 60 are found in Tables 3.2 and 3.3, respectively. Further details, including atomic coordinates, distances and angles are found in the CIF files in Appendix

2. For 60, one disordered toluene molecule was modeled by location of the non- hydrogen atoms from the difference fourier map. The model was refined with constraints on the bond distances and atomic displacement parameters. Hydrogen atoms of the toluene molecule could not be modeled.

Table 3.1. Crystal data and structure refinement details of 58 and 60·C7H8

58 60·C7H8

Formula C45H54N4OZr C36.5H37N3Zr Fw 758.14 608.91 Cryst. Syst monoclinic tetragonal

Space group P21/c I41/a a, Å 21.814(3) 22.1251(18) b, Å 18.146(2) 22.1251(18) c, Å 27.820(3) 24.479(3) α, deg 90.00 90.00 β, deg 110.216(2) 90.00 γ, deg 90.00 90.00 V, Å3 10334(2) 11982.7(19) Z 8 16 -3 Dcalcd, g cm 0.975 1.350 T, °C 133 123 μ, mm-1 0.242 0.397 λ, Å 0.71073 0.71073 transm coeff 1.00-0.830 1.00-0.848 2θ limits, deg 1.98-63.48 2.48-60.28 total no. of data 93808 51513 no. unique data 32334 8825 no. obsd data 26138 7717 no. of params 1617 529

R1 (I > 2σ(I)) 0.0820 0.0432 2 wR2 (I , all data) 0.2313 0.1151 max, min peaks, e/Å3 2.525, 0.644, a b c 2 2 2 2 2 1/2 I > 2σ(I). R1 = | |Fo| – |Fc| | / |Fo|. wR2 = [ [w (Fo – Fc ) ] / [w (Fo ) ]] .

3.4 Results and Discussion

Constrained geometry complexes are typically synthesized through two synthetic routes: 1) salt metathesis or 2) amine elimination. Salt metathesis reactions traditionally occur via deprotonation of a CGC ligand with an alkyllithium reagent and subsequent reaction with a metal chloride.4,47,104,135 Although this method allows for isolation of a constrained geometry chloro complex, the final product needs to be separated from the lithium salt produced in these reactions. Isolated yields from this route vary depending on the system, with moderate yields (40-70%) commonly reported.

Formation of CGCs via amine elimination has several advantages. Zirconium and titanium tetrakisdialkylamido reagents used in amine elimination reactions are readily synthesized by lithiation of dialkylamine and subsequent reaction with the appropriate metal chloride in THF. Formation of CGCs via amine elimination reactions is synthetically straightforward since the eliminated amine can be removed in vacuo. This usually results in relatively facile product isolation and high yields.126,136

Initial investigations into the preparation of CGCs with H3FDI via salt metathesis proved unsuccessful. Deprotonation of the fluorenyl moiety was attempted with nBuLi,

NaH, and Schlosser‟s Base (KOtBu/nBuLi) under various reaction conditions.

Deprotonation attempts were made in THF and diethyl ether at cold temperature and room temperature. Reaction times spanned from a few hours to several days. Solid compounds were isolated by either precipitation with hexanes or removal of solvents after appropriate workup. In most cases, a mixture of unidentified products was obtained, and deprotonation of the fluorene proton of the five-membered ring was not observed.

n Attempts were also made to isolate the deprotonated forms of H3FDI using BuLi, NaH,

Na metal, and Schlosser‟s Base via reaction in THF or diethyl ether and precipitation with hexanes. In all cases, it was unclear by NMR characterization if deprotonation of the fluorenyl moiety occurred. This turned our attention to the amine elimination route.

Therefore, amine elimination was chosen as the preferential route for the formation of group 4 metal complexes.

3.4.1 Preparation and Characterization of (HFDI)M(NEt2)2 (M = Zr, Ti)

Complex 58 ((HFDI)Zr(NEt2)2(THF)) was synthesized by reaction of Zr(NEt2)4 and H3FDI in toluene. After refluxing for two hours, the reaction mixture was stirred for twelve hours at room temperature (eq. 1). After solvent removal and recrystallization from a concentrated THF solution, complex 58 was isolated in 80% yield as pale yellow crystals.

O N toluene N(CH2CH3)2 (1) Zr(NEt2)4 + H3FDI Zr

N N(CH2CH3)2

The 1H NMR spectrum of 58 confirmed a bidentate structure of the HFDI ligand.

Resonances and integration ratios of amido methylene and methyl resonances as well as the HFDI resonances indicate two amido groups per HFDI ligand and suggest a monometallic complex (Figure 3.1). The absence of NH protons in the NMR spectrum confirms that the two indolyl moieties are coordinated to the zirconium center. The

75 presence of the fluorenyl proton of the five-membered ring produces a triplet at 4.28 ppm and indicates that the fluorenyl moiety is not deprotonated nor 5-coordinated. The methylene protons of the ligand backbone appear as a doublet of doublets, also indicating that the fluorenyl proton is present. The presence of two sets of resonances for the diethyl amido groups is also observed, as well as two resonances at 3.66 and 1.24 ppm for one coordinated THF molecule. Specific assignments for these resonances were aided by 2D gCOSY, gHMQC and gHMBC experiments. For the indolyl moieties, two doublet resonances were observed at 7.72 and 7.62 ppm for H7 and H4, respectively.

Two triplet resonances were observed at 7.33 and 7.32 ppm for H6 and H5, respectively.

There was a singlet resonance at 2.29 ppm, which integrates to six protons for the indolyl methyl groups. The presence of one single resonance for the methyl groups suggests a symmetrical structure in solution. For the fluorenyl moiety, two doublet resonances are observed at 7.47 and 7.36 ppm for H4 and H1, respectively. There were two triplet resonances at 7.19 and 7.06 ppm for H3 and H2, respectively. There was a triplet resonance at 4.28 ppm for the fluorenyl proton of the five-membered ring. A triplet resonance is also observed for the methine proton at 5.04 ppm. Two distinct sets of resonances are observed for two diethyl amido groups on the zirconium metal center. A sharp quartet is observed at 3.46 ppm, and one broad quartet is observed at 3.24 ppm for the methylene protons of the ethyl groups. Two sharp triplet resonances are observed at

0.86 and 0.55 ppm for the methyl protons of the ethyl groups. Integrations of these resonances reveals two separate diethylamido moieties. The coordinated THF molecule was observed as broad multiplets, suggesting a dynamic process in solution. The

76 presence of a coordinated THF molecule was confirmed by X-ray structural analysis.

This type of interaction was also observed by Fneich in related zirconium compounds.98

3 2 4 1

O N N(CH2CH3)2 Zr

N N(CH2CH3)2

4 6 58 5

indo-H6/H5 indo-H4 flu-H1 flu-H3 indo-H7 flu-H2 flu-H4

indole-CH3

amido-CH3

amido-CH2 THF THF

CH2 CH flu-CH

Figure 3.1. 1H NMR spectrum of 58. The top spectrum is of the aromatic region of 58.

Crystals of 58 were grown from a concentrated THF solution at 30 °C and analyzed by X-ray crystallography. Crystallographic data confirmed the bidentate structure of 58 proposed by NMR methods, as well as a symmetrical structure and a non- coordinated fluorenyl moiety (Figure 3.2). For the preliminary solution of the structure,

1 13 space group P21/c was chosen. As proposed by H and C NMR data, there is one THF molecule coordinated to the zirconium metal center. Zirconium-amido bond distances for

Zr(1) N(3) and Zr(1) N(4) are 2.012(2) Å and 2.038(2) Å respectively, and are in the range (2.013-2.019 Å) of other reported zirconium-amido distances.98 A relatively short metal-amido bond distance, as well as trigonal planar geometry of the amido nitrogens, suggest -donation of the nitrogen lone pair to the metal center. Zirconium-indolyl bond distances for Zr(1) N(2) and Zr(1) N(1) are 2.194(2) Å and 2.201(2) Å, respectively, and are in the range (2.19-2.21 Å) of reported zirconium-indolyl distances.98

The elongated metal-indolyl bond distance is consistent with reduced N M donation due to the delocalization of the nitrogen lone pair into the aromatic system. Coordination of one THF molecule is confirmed with a Zr(1) O(1) bond distance of 2.2841(19) Å, which is in the range observed for other related complexes.98

Figure 3.2. ORTEP diagram of 58. Thermal ellipsoids are drawn at the 30%

probability level. Hydrogen atoms are omitted for clarity.

Table 3.2. Selected bond distances and angles for complex 58. ______Bond distances (Å) Zr1 N1 2.201(2) Zr1 N4 2.038(2) Zr1 N2 2.194(2) Zr1 O1 2.2841(19) Zr1 N3 2.012(2)

Bond angles (deg) C50 N3 52 115.2(2) N1 Zr1 N2 83.77(8) C60 N4 C62 115.1(2) N3 Zr1 N4 109.46(10) C20 N2 C27 105.0(2) C10 N1 C17 105.5(2) ______

Several attempts were undertaken to drive another amine elimination and deprotonate the fluorenyl moiety of 58 for 5-coordination to the zirconium center. After isolation of pure 58, a small portion of the solid was dissolved in benzene-d6 and placed in a sealed NMR tube. No changes in the NMR were observed when this tube was heated

79 to 80 °C for 20 h. Further heating to 90-100 °C did not result in any changes in the 1H

NMR spectrum. Another small sample was dissolved in THF and refluxed for 12 h, and only decomposition products and starting materials were observed by 1H NMR spectroscopy. Another small sample was dissolved in xylenes and refluxed for 12 h. A green solid formed, which was insoluble in chloroform-d and benzene-d6, indicating possible decomposition. A small sample of 58 was dissolved in THF, and one equivalent of n-butyllithium was added, turning the reaction solution red. After stirring for 12 h at room temperature, solvents were removed in vacuo, and the 1H NMR spectrum revealed no identifiable products. Another small sample of 58 was dissolved in THF and an excess of diazabicycloundecene (DBU) was added to the reaction solution. No observable change was detected by 1H NMR spectroscopy after stirring at room temperature for 12 h, so the mixture was then refluxed 12 h. Removal of solvents and analysis by 1H NMR revealed only unreacted starting materials.

Unsuccessful removal of a fluorenyl proton of a carbon bridged ligand via amine elimination has been documented before.137 The relative acidity of this fluorenyl proton

(pKa = 22.3) is known to be lower in comparison to related indenyl (pKa = 21.8) and

138 cyclopentadienyl moieties (pKa = 18.0). It is known that the fusion of benzene rings to a cyclopentadienyl moiety typically decreases the acidity of the remaining protons of the five-membered ring. Furthermore, 5-coordination of the fluorenyl moiety may be hindered due to steric congestion in this ligand system.

Complex 59 ((HFDI)Ti(NEt2)2) was prepared using a method similar to that used for the preparation of 58. Equimolar reaction of Ti(NEt2)4 and H3FDI in toluene and

80 refluxing for three days produced (HFDI)Ti(NEt2)2 as a red-orange solid after removal of solvents in vacuo in 46% yield (eq. 2).

N N(CH CH ) toluene 2 3 2 Ti(NEt2)4 + H3FDI Ti (2) N N(CH2CH3)2

In every case, complex 59 was isolated with a small percentage of free ligand. Repeated attempts to separate these two compounds through crystallization proved unsuccessful.

NMR analysis and integration of the observed resonances confirmed the bidentate structure of the HFDI ligand, analogous to that of complex 58. The absence of indolyl proton resonances indicates that the two indolyl moieties are coordinated to the titanium center, and the presence of the fluorenyl proton of the five-membered ring indicates that the fluorenyl moiety is not coordinated. Two separate sets of resonances were observed for two diethylamido moieties. In contrast to 58, complex 59 does not feature a coordinated THF, even after attempts to recrystallize 59 from concentrated solutions in

THF. This was also observed in related titanium compounds prepared by Fneich,98,102 and is consistent with the smaller size of titanium (ionic radii: Ti4+ = 60.5 pm, Zr4+ = 72 pm). For the indolyl moieties, two doublet resonances were observed at 7.60 and 7.50 ppm for H7 and H4, respectively. Two triplet resonances were observed at 7.28 and 7.25 for H6 and H5, respectively. A singlet resonance was observed at 2.11 ppm, which integrates to six protons for the methyl groups of the indolyl moieties. The appearance of

81 one resonance for the indolyl methyl groups indicates a symmetrical structure in solution.

For the fluorenyl moiety, two doublet resonances were observed at 7.46 and 7.36 ppm for

H4 and H1, respectively. Two triplet resonances appear at 7.17 and 7.04 ppm for H3 and

H2, respectively. A triplet resonance for the proton of the fluorenyl five-membered ring was shown at 4.04 ppm, indicating a non-coordinated fluorenyl moiety. A triplet resonance was observed at 4.88 ppm for the methine proton. Two sharp quartet resonances were observed for the methylene protons of the two amido groups at 3.68 and

3.42 ppm, as well as two triplets at 1.10 and 0.68 ppm for the methyl groups of the amido moieties. Repeated attempts to crystallize 59 for X-ray crystallographic analysis from concentrated solutions of toluene, THF, methylene chloride or mixtures of these solvents with hexanes proved unsuccessful.

3.4.2 Preparation and Characterization of (IDI)Zr(NEt2)

Complex 60 was prepared by reaction of Zr(NEt2)4 and H3IDI in toluene. After refluxing for two hours, the reaction solution was cooled to room temperature and filtered to remove a small amount of insoluble solid that was formed in the reaction. After removal of solvents, the resulting brown residue was recrystallized from hot toluene, and complex 60 was isolated as pale yellow crystals in 55% yield (eq. 3).

toluene H (3) Zr(NEt2)4 + H3IDI Zr N NEt2 N

Analysis of 60 by 1H and 13C NMR spectroscopy revealed a constrained geometry complex with two indolyl moieties coordinated to the zirconium center as well as 5-

82 coordination of the indenyl moiety. Integration of the 1H NMR resonances indicated two indolyl moieties for each indene. Specific assignments of the 1H and 13C NMR resonances were aided by gCOSY, gHMQC, and gHMBC experiments. For the indolyl moieties, two separate sets of resonances were observed, indicating inequivalent indolyl moieties (Figure 3.4). Two doublet resonances were observed at 7.85 and 6.46 ppm for the two H7 protons. A doublet resonance was seen at 7.40 ppm and a multiplet resonance was observed at 7.07 ppm for the two H4 protons. Four total triplet resonances were observed at 7.07 and 6.93 ppm for H6, and 7.02 and 6.58 ppm for H5. Two singlet resonances were seen at 2.45 and 2.44 ppm for the two methyl groups of the indolyl moieties. There was one set of resonances observed for the indenyl moiety, with two doublet resonances at 7.44 and 6.23 ppm for H4 and H7, respectively, as well as two triplet resonances at 7.02 and 6.81 ppm for H5 and H6, respectively. There were two doublet resonances for the indenyl protons of the five-membered ring at 6.85 and 6.13 for

H2 and H3, respectively. Significant shifting of these proton resonances as well as the absence of the indenyl H1 proton indicated 5-coordination of the indenyl moiety. A doublet of doublets resonance was observed at 5.35 ppm for the methine proton, and two doublet of doublets resonances were observed at 3.58 and 3.37 ppm for the diastereotopic methylene protons, which is indicative of an ABX splitting pattern (Figure 3.4). A single set of resonances was seen for one diethylamido moiety coordinated to the zirconium center. A multiplet was observed for the diasterotopic methylene protons of the amido moiety at 3.90 ppm, and a triplet resonance was seen at 1.24 for the methyl protons of the amido moiety.

H Zr N NEt2 N

- H6

H2 toluene H3 H7 - H7 H6 H4 - H7 - H4 - - - H4 - - indo - H5 H6 indo - - inde ndo inde i ndo indo indo indo inde i inde indo inde

Figure 3.3. 1H NMR spectrum of the aromatic region of 60.

toluene

indole-CH3

amido-CH3

CH amido-CH2

CH2

Figure 3.4. 1H NMR spectrum of the aliphatic region of 60.

Crystals of 60 were grown from a concentrated toluene solution at 30 °C and analyzed by X-ray crystallography. Crystallographic analysis confirms the coordination of both indolyl moieties as well as the 5-coordination of the indenyl moiety, and

84 confirms the structure of 60 as proposed by NMR methods (Figure 3.6). The structure

1 13 was solved in space group I41/a. As proposed by H and C NMR data, there is one amido moiety bound to the zirconium metal center. The zirconium-amido bond distance for Zr(1) N(3) is 2.0060(17) Å. This bond distance is relatively short, and a trigonal planar geometry of the amido nitrogen suggests -donation of the nitrogen lone pair to the metal center. The sum of the angles around N3 of the amido moiety is 359.81°.

Zirconium-indolyl bond distances for Zr(1) N(1) and Zr(1) N(2) are 2.1109(17) Å and

2.1597(16) Å, respectively, and are in the range of reported zirconium-indolyl distances

(2.19-2.21 Å).98 The elongated metal-indolyl bond distance is a result of delocalization of the nitrogen lone pair into the aromatic ring, and reduced N M donation. The average zirconium-carbon distance for Zr(1) C(3), Zr(1) C4, Zr(1) C(5), Zr(1) C(30), and Zr(1) C(35) of the indenyl five-membered ring is 2.4891(38) Å, and is comparable to that of other known indenylzirconium CGCs (2.5303(17) Å).139 The bond distances are relatively similar to each other, and indicate 5-coordination of the indenyl moiety. A short bond distance from the zirconium metal center to the methylene carbon of the amido moiety, Zr(1) C(8), of 2.6961(19) Å is within the range of reported agostic interactions of similar compounds.98

Figure 3.5. ORTEP diagram of 60. Thermal ellipsoids are drawn at the 30%

probability level. Hydrogen atoms are omitted for clarity.

Figure 3.6. ORTEP diagram of the zirconium core of 60. Thermal ellipsoids are

drawn at the 30% probability level. Hydrogen atoms, a toluene solvate

molecule, and the indolyl moieties are omitted for clarity.

Table 3.3. Selected bond distances and angles for complex 60 ______Bond distances (Å) Zr1 N1 2.1109(17) Zr1 C3 2.4346(18) Zr1 N2 2.1597(16) Zr1 C4 2.4795(19) Zr1 N3 2.0060(17) Zr1 C5 2.501(2) Zr1 C8 2.6961(19) Zr1 C30 2.4903(18) Zr1 C35 2.5400(19)

Bond angles (deg) N1 Zr1 N2 91.62(6) C10 N1 Zr1 115.57(12) N1 Zr1 N3 111.61(7) C20 N2 Zr1 114.37(12) N2 Zr1 N3 122.58(6) C10 C1 C20 115.39(16) C10 N1 C17 106.07(17) C20 N2 C27 105.40(15) ______

Structural analysis of 60 by X-ray crystallography suggests a 14-electron zirconium complex. Six electrons are donated to the metal center from the 5-indenyl moiety, and two electrons each are donated from the indolyl moieties. Four electrons are also donated to the metal center by the amido moiety. Also indicated by the X-ray structural analysis is the open space below the zirconium center. Accessibility of the metal center should allow enough room for substrate coordination for catalytic applications.

3.4.3 Preparation and Characterization of (FDI)M(CH3) (M = Zr, Ti)

Constrained geometry methyl complexes were prepared using an analogous

48 method to that reported by Resconi et al. Reaction of H3FDI (51) with four equivalents

87 of methyllithium in diethyl ether and subsequent reaction of this mixture with the appropriate metal chloride in diethyl ether afforded complexes 61 and 62 in moderate yields (eq.4).

1) 4 MeLi

2) MCl4(THF)2 (s) H M H3FDI N (4) CH3 Et2O N

M = Zr (61), Ti (62)

Complex 61, (FDI)Zr(CH3), was isolated as a red-orange solid in 55% yield.

Analysis of 61 by 1H and 13C NMR spectroscopy suggested an 5-coordinated fluorenyl moiety and two coordinated indolyl moieties (Figure 3.7). For the indolyl moieties, two doublet resonances were observed at 7.44 and 6.27 ppm for H4 and H7, respectively.

There were two triplet resonances at 6.97 and 6.86 ppm for H5 and H6, respectively. A singlet resonance at 2.55 ppm which integrated to six protons was seen for the indolyl methyl groups. The presence of only one resonance for these methyl groups suggests a symmetrical structure in solution. For the fluorenyl moiety, two doublet resonances were observed at 7.97 and 7.27 ppm for H4 and H1, respectively, as well as two triplet resonances at 7.18 and 6.65 ppm for H3 and H2, respectively. For the ligand backbone, there was a triplet resonance at 5.20 ppm for the methine proton, and a doublet resonance which integrates to two protons for the methylene protons at 3.64 ppm. In the free ligand, these methylene protons were observed as a doublet of doublets when the fluorenyl proton is present. Also observed in the 1H NMR spectrum were broad THF resonances at 3.42 and 1.55 ppm, and broad Et2O resonances at 3.10 and 1.16 ppm, which suggest coordinative bonding to the zirconium center. Attempts to isolate 61 free

88 of these coordinating solvents in vacuo were unsuccessful. In many cases, decomposition was observed after long periods of drying under vacuum. A singlet resonance was observed for the zirconium-methyl group at 0.42 ppm, which is in the range ( 0.74-0.24 ppm) of values for reported zirconium-methyl complexes.48,140 Repeated attempts to obtain crystalline material of this complex for X-ray analysis with concentrated solutions of toluene, THF, methylene chloride, diethyl ether, or mixtures of these solvents with hexanes were unsuccessful. It should be noted that 61 is stable under nitrogen atmosphere, but decomposes rapidly to a purple solid upon exposure to air.

H Zr N CH3 N

indo-H1 indo-H5 flu-H2

flu-H4 indo-H4 flu-H3 indo-H6 indo-H7

indole-CH3 Zr-CH3

Et2O Et2O

THF grease CH2 THF CH

Figure 3.7. 1H NMR spectrum of 61. The top spectrum is of the aromatic region.

Complex 62, (FDI)Ti(CH3), was prepared using an analogous method to that of

61. Complex 62 was isolated as a brown/black solid after appropriate workup in 36%

1 13 yield. Formation of (FDI)Ti(CH3) was indicated by H and C NMR spectra that were similar to those for (FDI)Zr(CH3). Appearances and integrations of the proton resonances indicated two indolyl moieties coordinated to the titanium center as well as

5-coordination of the fluorenyl moiety. For the indolyl moieties, two doublet resonances were observed at 7.27 and 6.27 ppm for H4 and H7, respectively. There were two triplet resonances at 6.92 and 6.84 ppm for H5 and H6, respectively. One singlet resonance which integrated to six protons was seen at 2.44 ppm, which indicated a symmetrical sturture in solution. For the fluorenyl moiety, two doublet resonances were observed at 8.23 and 6.67 ppm for H4 and H1, respectively. There were two triplet resonances at 7.17 and 6.78 ppm for H3 and H2, respectively. The absence of the fluorenyl proton of the five-membered ring indicates 5-coordination of the fluorenyl moiety. There was a triplet resonance at 5.26 ppm for the methine proton, and a doublet resonance which integrated to two protons at 3.75 ppm for the methylene protons. A singlet resonance was observed at 0.30 ppm for the titanium-methyl group. The presence of broad THF resonances at 3.48 and 1.69 ppm and sharp resonances of Et2O at 3.46 and

1.19 ppm indicated coordinative bonding to the titanium center. Attempts to isolate 62 free of these coordinating solvents were unsuccessful. It should be noted that while the reproducibility of the synthesis of (FDI)Zr(CH3) (61) is high, the preparation of

(FDI)Ti(CH3) (62) is sensitive and is not easily reproducible.

3.4.4 Preparation and Characterization of (IDI)Nb(=NR)x (py)x; ( = 0, 1)

Niobium imido reagents are readily synthesized according to published

131,132 t procedures (eq. 5). Two reagents were synthesized, ( BuN)NbCl3(py)2 and

(PhN)NbCl3(dme) which were used in the preparation of constrained geometry metal- imido complexes. Initial attempts to synthesize CGCs with niobium pentachloride were unsuccessful, and therefore niobium-imido reagents were used in order to prepare complexes 63 and 64. While these reactions work moderately well with H3IDI, analogous attempts to synthesize niobium-imido complexes with H3FDI were unsuccessful.

t toluene t NbCl5 + BuNH2 + Me3SiCl ( BuN)NbCl3(py)2 (5) pyridine

t Complex 63, (IDI)Nb(N Bu)(py), was prepared by deprotonation of H3IDI with

t methyllithium in diethyl ether, and subsequent reaction with ( BuN)NbCl3(py)2 in toluene

(eq. 6). After appropriate workup, complex 63 was isolated in 80% yield as a purple solid.

1) 3 MeLi Et O H 2 Nb t H3IDI N N Bu (6) t 2) (py)2Cl3Nb=N Bu N N toluene

Analysis of complex 63 by 1H and 13C NMR spectroscopy revealed two sets of resonances for two inequivalent indolyl moieties and one indenyl moiety (Figure 3.9).

The two indolyl moieties were coordinated to the niobium center as well as one 5- coordinated indenyl moiety. A single imido moiety on the niobium center and one coordinated pyridine molecule were also detected. For the indolyl moieties, a total of four doublet resonances were observed. There were two doublet resonances at 7.90 and

7.38 ppm for H4 and two doublet resonances at 7.32 and 6.52 ppm for H7. A total of four triplet resonances were also present. Two triplet resonances were seen at 7.26 and

7.16 ppm for H5, and two additional triplet resonances at 7.08 and 6.96 ppm for H6.

There were two singlet resonances for the indolyl methyl groups at 2.44 and 2.41 ppm which integrate to three protons each. For the indenyl moiety, one doublet resonance was observed at 7.58 ppm for H4, and one multiplet resonance at 6.67 ppm for H7. There were two triplet resonances at 7.12 and 6.89 ppm for H5 and H6, respectively.

Integration and the number of observed resonances indicated a monometallic species.

1 Analogous to the H NMR resonances reported for (IDI)Zr(NEt2) (60), a doublet of doublets resonance was observed at 5.32 ppm for the methine proton, and two doublet of doublets resonances were seen at 3.48 and 3.20 ppm which is indicative of an ABX splitting pattern for the diastereotopic methylene protons. A singlet resonance was observed at 1.53 ppm which integrated to nine protons, downfield shifted from that of the niobium starting material (1.45 ppm).

H Nb N NtBu N N

=N-tBu

toluene

Indole-CH3

CH CH2

Figure 3.8. 1H NMR spectrum of the aliphatic region of 63.

Complex 64, (IDI)Nb(NPh), was prepared in two steps by reaction of H3IDI with three equivalents of methyllithium in diethyl ether, followed by subsequent reaction with

(PhN)NbCl3(dme) in toluene. After stirring at room temperature for 12 h and proper workup, (IDI)Nb(NPh) was isolated as a dark red solid. Characterization of complex 64 was assisted by 1H NMR analysis, which gave spectra analogous to those of 63. The absence of resonances for DME from the niobium starting material suggested that DME is not coordinated to the metal center. Complete characterization of complex 64 was hindered by overlap and broadening of the aromatic region. Several resonances of the indolyl, indenyl, and phenylimido moieties appeared as broad multiplets. The absence of

93 the indenyl H1 proton suggested 5-coordination of the indenyl moiety. The indenyl protons of the five-membered ring, H3 and H2, were shifted from those of the free ligand.

These two protons were observed as doublet resonances at 7.03 and 6.16 ppm, respectively. A doublet of doublets resonance was seen at 5.63 ppm for the methine proton. Two doublet of doublets resonances were observed at 3.56 and 3.30 ppm for the methylene protons, which is indicative of an ABX splitting pattern similar to complex 63.

Two singlet resonances were seen for inequivalent methyl groups of the indolyl moieties at 2.47 and 2.45 ppm. It should be noted that while the preparation of 63 is very reproducible, the preparation of 64 is not easily reproducible. Several attempts to purify this complex by recrystallization from concentrated solutions of toluene, THF, methylene chloride, or mixtures of these solvents with hexanes were unsuccessful.

3.4.5 Titanium-Imido Complexes of Di(3-methylindolyl)methanes

Titanium-imido reagents are readily synthesized according to published procedures.133,134 The preparation of titanium-imido complexes 65, 66, and 67 was

t achieved via reaction of ( BuN)TiCl2(py)3 with lithiated di(3-methylindolyl)methanes (eq.

7). The synthesis of complex 65 gave good yields, but the preparation of complexes 66 and 67 worked only in moderate to low yield.

1) 2 nBuLi NH HN toluene 65, 66, 67 (7) t 2) ( BuN)TiCl2(py)3 R H

OCH N 3 CH R = NN 3

N H H H N O CH3 N t t t N Ti N Bu N Ti N Bu N Ti N Bu N N N N N N

65 66 67

Complex 65 was isolated as a red microcrystalline solid in 62% yield. The connectivity of complex 65 was confirmed by 1H and 13C NMR spectroscopy, which indicated that the two indolyl moieties were coordinated to the titanium center and one t- butylimido moiety was bound to the metal center. The presence of a single resonance for the indolyl methyl groups indicated a symmetrical structure in solution. NMR spectroscopic characterization also indicated one free pyridine molecule coordinated to the titanium center. For the indolyl moieties, two doublet resonances were observed at

7.35 and 7.03 ppm for H7 and H4, respectively. Two triplet resonances were seen at 6.81 and 6.63 ppm for H6 and H5, respectively. There is one singlet resonance at 2.55 ppm which integrated to six protons for the indolyl methyl groups. For the pyridyl moiety, two doublet resonances were observed at 7.39 and 7.28 ppm for H11 and H8, respectively. Two triplet resonances were seen at 7.48 and 7.24 ppm for H10 and H9, respectively. A singlet resonance which integrated to one proton was observed at 6.09 ppm for the methine proton. There was a singlet resonance seen at 1.17 ppm which integrated to nine protons for the t-butylimido moiety. Several attempts were made to obtain X-ray quality crystals through recrystallization from concentrated toluene, THF, and methylene chloride, but only microcrystalline materials were isolated in each case.

Slow recrystallization at room temperature or through evaporation also resulted in

95 microcrystalline material. X-ray analysis was attempted with a suitable microcrystal, and while the connectivity of the metal complex was confirmed, repeated attempts at complete modeling of 65 were unsuccessful. The raw X-ray data were analyzed with

Gemini, as the crystal appeared to be twinned. Two coordinated pyridine molecules were observed in the preliminary solution of the data, and the pyridyl moiety appeared to not be coordinated to the titanium center.

Complex 66 was prepared by a similar method to that for 65.

(Methoxyphenyl)di(3-methylindolyl)methane was deprotonated with n-butyllithium, and

t subsequently reacted with ( BuN)TiCl2(py)3 in toluene. After refluxing for 12 h and appropriate workup, complex 66 was isolated as a dark yellow microcrystalline material in 45% yield. Analysis of 66 by 1H NMR spectroscopy showed analogous resonances to those observed for 65. NMR characterization revealed that the two indolyl moieties and the methoxyphenyl moiety were coordinated to the titanium center, and one pyridine molecule was also coordinated. A broad resonance is observed for the methyl groups of the indolyl moieties, which integrated to six protons. Variable temperature analysis of this resonance revealed a sharpened singlet at 40 °C (Figure 3.9). Separation of the two methyl groups was observed at 30 °C, and integration of these two resonances suggested three protons for each singlet. This is indicative of a dynamic process in solution which was most likely the result of the orientation of the methyl group of the methoxyphenyl moiety.

9 10 8 11 H O CH3 t N Ti N Bu N N 4 7 5 6

indole-CH3 t OCH3 N- Bu 40 °C 30 °C 20 °C 10 °C 0 °C –10 °C –20 °C –30 °C

Figure 3.9. Variable temperature 1H NMR stack-plot spectra of 66.

For the aromatic resonances of the indolyl moieties, a doublet resonance was observed at

7.42 ppm for H7 and a multiplet resonance was seen at 7.11 for H4. A triplet resonance was observed at 7.59 ppm for H6, and a broad multiplet was seen at 7.04 ppm for H5.

For the aryl resonances of the methoxyphenyl moiety, triplet resonances were seen at

7.19 and 6.93 ppm for H4 and H3, respectively. A broad multiplet resonance is observed at 7.12 ppm for H5, and H2 appeared as a doublet resonance at 6.80 ppm. The methoxy resonance appeared as a broad singlet at 3.07 ppm, which integrates to three protons. A singlet resonance was observed at 6.01 ppm for the methine proton, and another singlet, which integrated to nine protons, was seen at 1.17 ppm for the t-butylimido moiety.

Integrations and the number of resonances indicated a monometallic species in solution.

Poor solubility of complex 66 in traditional NMR solvents hindered 13C NMR characterization. Repeated attempts to isolate crystals suitable for X-ray analysis from concentrated solutions of 66 in toluene, THF, or methylene chloride resulted in microcrystalline solid.

Complex 67 was synthesized using an analogous method to that used for complex

65. Reaction of lithiated (N-methylimidazolyl)di(3-methylindolyl)methane with t ( BuN)TiCl2(py)3 in toluene resulted in a brown reaction mixture. Proper workup of this reaction mixture after room temperature stirring for 12 hours afforded complex 67 as orange needle-like microcrystals in 25% yield. Analysis of this material by 1H NMR spectroscopy revealed a set of resonances similar to that of 65, consistent with the two indolyl moieties and the imidazolyl moiety coordinated to the titanium center. Two singlet resonances for the imidazolyl methyl and the indolyl methyl groups indicated a symmetrical structure in solution. For the aromatic resonances of the indolyl moieties, two doublet resonances were observed at 7.62 and 7.42 ppm for H7 and H4, respectively.

There were two triplet resonances at 6.92 and 6.85 ppm for H6 and H5, respectively. For the indolyl methyl groups, a singlet resonance which integrates to six protons was seen at

2.45 ppm. The imidazolyl protons appeared as doublet resonances at 6.78 and 6.71 ppm for H4 and H5, respectively. A singlet resonance integrating to three protons was observed at 3.48 ppm for the imidazolyl methyl group. A singlet resonance which integrated to nine protons was seen at 1.14 ppm for the t-butylimido moiety. Poor solubility of complex 67 in traditional NMR solvents hindered characterization by 13C

NMR. Repeated attempts to isolate crystals suitable for X-ray analysis from concentrated solutions of toluene, THF, and methylene chloride resulted in the formation of

98 microcrystalline material. Attempts at slow room temperature recrystallization or crystallization by evaporation were unsuccessful.

3.5 Conclusions

The synthesis and characterization of a new series of bidentate, constrained geometry, and related complexes is reported. Syntheses of (HFDI)Zr(NEt2)2(THF) (58) and (HFDI)Ti(NEt2)2 (59) are relatively straightforward, and proceed in high to moderate yields. These complexes are similar to those reported by Fneich,98 and deprotonation of the fluorenyl proton via amine elimination was not successful. Synthesis of

(IDI)Zr(NEt2) (60) via amine elimination is reproducible and proceeds in moderate yields. This complex is the first example of a CGC with an indolyl-based ligand.

Syntheses of (FDI)Zr(CH3) (61) and (FDI)Ti(CH3) (62) using methyllithium proceeded to give moderate yields, and are the first examples of CGC methyl complexes with indolyl- based ligands. The preparation of (IDI)Nb(NtBu)(py) (63) is reproducible and proceeds in high yields. The preparation of (IDI)Nb(NPh) (64) is less straightforward, and the complex is difficult to fully characterize by spectroscopic methods. These complexes represent the first examples of group 5 imido constrained geometry complexes with indolyl-based ligands. The synthesis and characterization of titanium-imido complexes with di(3-methylindolyl)methane ligands are reported. (tBuN)Ti{(2-pyridyl)di(3- methylindolyl)methane} (65), (tBuN)Ti{(2-methoxyphenyl)di(3-methylindolyl)methane}

(66), and (tBuN)Ti{(N-methylimidazolyl)di(3-methylindolyl)methane} (67) were isolated as microcrystalline solids in moderate yields. These complexes represent the initial

99 studies of group 4 imido complexes with diindolylmethane ligands, and could be potentially useful in catalytic applications.

100

Chapter Four

Olefin Binding Studies of Copper(I) Pyridine Derivative Complexes

4.1 Introduction

According to Chemical & Engineering News, ethylene and propylene consistently occupy the top two positions on the list of organic chemicals produced annually.141 From

1997-2007, ethylene production averaged 24.2 billion metric tons per year, while propylene production averaged 14.3 billion metric tons per year. For comparison, the organic chemical produced in the third largest quantity was ethylene dichloride, averaging 10.4 billion metric tons over the same time period. Ethylene is currently used in huge quantities as a starting material in a variety of chemical processes such as polymerization, oxidation, halogenation, alkylation, hydration, oligomerization, and oxo- reactions.142 The products obtained from these processes can then be used as intermediates towards compounds found in fibers, packaging products, plasticizers, cleaning solvents, automotive parts, and adhesives, to name a few. Large production processes such as these benefit greatly from reducing production costs both monetarily and energetically. Therefore, a cost or energy efficient method of producing ethylene and propylene is potentially very attractive to industrial companies.

The vast majority of ethylene and propylene feedstocks are produced from thermal or catalytic cracking of crude oil.143 After cracking, a fraction composed of low

101 molecular weight alkanes, alkenes, and alkynes along with by-products such as water, sulfur-containing compounds, carbon monoxide and carbon dioxide is generated.

Thermal fractionation is then used to produce fractions composed of chemicals with similar boiling points, but complicated separation is needed to isolate individual compounds. Currently, cryogenic distillation is used to separate ethylene from ethane and propylene from propane, all of which are found in the volatile fraction.144 Although cryogenic distillation has been used for many years, it is a very energy intensive and economically expensive method for the separation of these chemicals.145 Therefore, finding an alternative to this method could be advantageous. There are several ongoing investigations into processes that utilize olefin transport via chemical complexation rather than separating these components via differences in volatility.146 The major aim of these methods is to eliminate the mass energy consumption and reduce the capital cost of the current processes. Currently, Sorbex®, a family of adsorptive materials, has been developed for commercial use by UOP.147 This technology utilizes a fixed bed of adsorbent to separate different fractions from the petroleum cracking process.

Olex® technology is an adsorptive material that is used to separate olefins from paraffins in a liquid-phase mixture.148 Contact of the adsorbent bed with the liquid-phase mixture selectively adsorbs olefins, thereby facilitating separation. This method utilizes a continuous flow of the liquid phase, whereas previous methods similar to this type used fixed-bed adsorption and were therefore slow to be incorporated commercially. The major advantage of this method over conventional extraction or extractive distillation techniques is the higher mass-transfer efficiency gained by using adsorptive methods.

102

Although Sorbex® technologies have improved separation, further improvements in cost effectiveness are needed.

Transition metal complexes of olefins are well studied in the literature. These complexes generally contain late transition metals, specifically the coinage metals copper and silver.149 This type of metal-olefin binding is traditionally described using the

Dewar-Chatt-Duncanson model of metal-olefin coordination (Figure 4.1).150,151 The bonding is described in two parts: 1) -donation of a filled -orbital of the olefin to an empty orbital on the metal, and 2) -back bonding from a filled d-orbital of the metal to the empty *-orbital of the olefin. The first complex known to exhibit olefin-metal binding was Zeise‟s salt, K[PtCl3(C2H4)], which was formed in a reaction between platinum(II) chloride and ethanol in 1827.152 It was not until 1951, however, that the bonding in this complex could be explained in detail. Dewar first hypothesized, based on molecular orbital theory, that the interaction of the molecular orbitals of the olefin and the atomic orbitals of the metal help stabilize the complex.150 Building on this explanation, Chatt and Duncanson used their experience with platinum(II) and palladium(II) complexes to explain that the metal is both a donor and an acceptor.151 This explanation evolved into the currently accepted Dewar-Chatt-Duncanson model of bonding in metal-olefin complexes.6

C C M M C C

-donation -backbonding

Figure 4.1. Dewar-Chatt-Duncanson model of bonding in transition metal-olefin

complexes.

103

Nickel is a late transition metal that has demonstrated the ability to form metal- olefin complexes. Wang and co-workers have shown that Ni[S2C2(CF3)2]2 reversibly binds olefins in a process that can be controlled electrochemically.153 Moreover, the olefin reacts with the dithiolene ligand instead of the nickel center (Figure 4.2). What is attractive about this system is the stability of the complex in the presence of typical poisons in the ethylene feedstock: carbon monoxide, hydrogen gas, and water. The nickel dithiolene complex was subjected to these poisons individually under conditions typical of ethylene binding, and no reaction was observed. This system can also be fine- tuned to maximize olefin separation and purification by adjusting temperature, pressure, and reaction media.153 However, this method is not cost effective because of the maintenance and construction of giant capacitors required for switching the potential of the system. Consequently, this system is not yet used industrially.

H2C CH2 F3C S S CF3 F3C S S CF3 Ni Ni

F3C S S CF3 F3C S S CF3

e- e- H2C CH2 - F3C S S CF3 Ni S S F3C CF3

Figure 4.2. Nickel(II) dithiolene system for electrochemical olefin separation.

104

Silver(I) complexes have been studied extensively and are known to form coordination complexes with various olefins.145,149,154 Early work by Eberz and coworkers has shown that simple systems like silver(I) nitrate can form a complex with isobutene in aqueous solution.155 Equilibrium constants that were calculated from the data suggest that the reaction heavily favors the product side, indicating that silver(I) readily binds isobutene. Data provided by Winstein and Lucas has shown that silver(I) nitrate and perchlorate will form complexes with olefins such as ethylene, trimethylethylene, 2-pentene, 1-hexene, cyclohexene, and propenylbenzene.156

Furthermore, these simple silver salts also form complexes with substrates such as dimethylbutadiene and biallyl. The work by Winstein and Lucas also indicated that other ions like copper(II) do not form coordination complexes with olefins.156

The methods developed by Lucas to bind olefins with silver nitrate have also been used in recent experiments that utilize transport membranes for the separation of 1- hexene and 1,5-hexadiene.157 Aqueous solutions (1.0 M) of silver nitrate are used as olefin carriers which are passed through Nafion® or Neosepta® membranes which allow for isolation of the free olefin.

Recently, complexes of silver(I) with tris(pyrazolyl)borate ligands (1) have been

149 used to bind olefins. Complexes with electron-rich MeB((3-Mes)Pz) 3 ligand are thermally stable solids. The steric bulk of the mesityl groups in the 3-position of the pyrazolyl moieties forms a pocket into which only small olefins and carbon monoxide can enter and bind. This small pocket allows for selective binding of smaller olefins over larger or branched olefins, which can lead to selective separation of mixed streams of

105 olefins. Although silver systems are very attractive for their affinity to bind olefins, these compounds are expensive and consequently not used for industrial scale separations.

CH3 B

N N N N N N Ag Mes Mes Mes H2C CH2 68

In the literature, binding of olefins to simple systems such as copper(I) chloride and copper(I) trifluoroacetate has been studied extensively.158-161 However, these substances have a tendency to polymerize and are typically stable only in the presence of excess olefin. One system uses copper(I) triflate under acidic conditions with excess vinyl sulfonate to separate olefins through an electrochemical process.162 The stability of this system in water makes it attractive to industry. Because copper(I) complexes of this type are typically insoluble in aqueous media, excess vinyl sulfonate is needed to stabilize the complex. These complexes, however, decompose slowly over many hours.

Furthermore, this complex has a tendency to reversibly bind acetylene and carbon monoxide, and reacts irreversibly with H2S, rendering it ineffective for olefin binding.

Consequently, this method is unsuitable for industrial use.

Nitrogen donor ligands have great potential for use in copper(I)-olefin complexes because of their ability to create stable complexes. Copper(I)-olefin complexes of multidentate nitrogen ligands are quite stable, easily characterized, and have been synthesized with a variety of polydentate ligands, such as diethylenetriamine (dien),163

164 165 1,10-phenanthroline (phen), and pentamethyldiethylenetriamine (Me5-dien).

Furthermore, simpler systems that use pyridine as a nitrogen donor group have proven

106 effective in olefin separation, are easily characterized, and are quite stable.166 Recently, the Averill Group has been interested in synthesizing copper(I) complexes of nitrogen donor ligands that selectively bind and release olefins. Systems that have been investigated are largely composed of neutral chelating nitrogen donor ligands that include pentamethyldiethylenetriamine (69),167 tris(2-pyridyl)carbinol (70),102 and tris(1- pyrazolyl)methane (71).102

CH3 CH3 H3C C C N CH3 N N N PF PF H C N CH 6 6 3 Cu 3 Cu Cu H3C N N PF6 N N N N N N C N N

CH3 OH H

69 70 71

Research by J.C. Davis and co-workers at BP Chemical has shown that copper- pyridine mixtures can bind and transport ethylene.166 Using various pyridine to copper nitrate ratios, Davis was able to control ethylene uptake in the system. Ethylene uptake was achieved using a solution of 1-2 M CuNO3 in 2-6 M aqueous pyridine. This system is attractive since it is highly soluble, and is stable for several days in the presence of H2 gas, a common poison of copper complexes found in petroleum feedstocks. These copper/pyridine systems, when tested using a membrane gas flux apparatus, can produce

>99% ethylene in a mixture of 3:1 ethane to ethylene with a flux of about 20 ft3/day/ft2 membrane. Although this method is very cost effective and efficient, it has some drawbacks. One drawback is the toxicity and volatility of pyridine used in the process,

107 and the other is the possible formation of explosive copper acetylides in basic solution, which arises from the presence of acetylene in petroleum feed stocks.

Previous work by J. C. Davis has shown that copper(I) pyridine complexes

+ ([Cu(py)2-3] ) possess a high uptake for ethylene, and are quite stable to the industrial process.166 Based on these results, Cu(I) complexes with substituted pyridine ligands were investigated for their ability to bind olefins. These complexes should have olefin binding affinities that do not differ greatly from pyridine, due to the functional group in the meta position. Substituted pyridines are less volatile and less toxic than pyridine, making their use in industry more attractive than the work by J. C. Davis. Target ligands in this study were 3-methoxypyridine (72), 3-hydroxypyridine (73), and methylnicotinate

(74). These ligands were used to synthesize complexes 75, 76, and 77, respectively.

Complexes were synthesized in varying pyridine derivative to copper ratios of 3:1, and tested for their olefin binding affinity. Focus was placed on the 3:1 complex to maximize the separation selectivity of the complex for smaller olefins in a mixture of small, terminal, and branched olefins. It should be noted that pyridine or substituted pyridines can compete for -backbonding due to sp2 hybridization of the nitrogen atoms, unlike sp3 hybridized amine ligands. Therefore, while olefin coordination was anticipated, equilibrium constant values were expected to be lower than those that utilize chelating amine ligands.

OCH3 OH C OCH3

N N N 72 73 74

108

CH3 C N R PF 6 OCH 75 Cu 3 OH 76 N N C(O)OCH 77 N 3

R R R

4.2 Experimental Section

General Considerations

All reactions were performed under an inert atmosphere of purified nitrogen using standard Schlenk techniques. Tetrahydrofuran and diethyl ether were distilled from sodium benzophenone ketyl prior to use. Toluene was distilled from sodium.

Acetonitrile and hexanes were distilled from calcium hydride prior to use. Chloroform-d, benzene-d6, and acetone-d6 were dried by storage over activated 4 Å molecular sieves.

Cuprous oxide was obtained from J.T. Baker and used without further purification. HPF6 was purchased as a 60% solution from Acros and used as received. Ethylene and propylene were purchased through Fisher Scientific in small gas cylinders, and 1-hexene, cis-3-hexene, and trans-3-hexene were purchased from Aldrich and used as received.

Methyl nicotinate, 3-methoxypyridine, and 3-hydroxypyridine were purchased from

Aldrich and used as received. Tetrakisacetonitrile copper(I) hexafluorophosphate was

168 synthesized from Cu2O, CH3CN, and HPF6 using a modified literature procedure.

Solution NMR spectra (1H, 13C, variable temperature) were recorded on Varian Gemini

200, Varian Unity 400, and Varian Inova 600 spectrometers using the deuterated solvent as the internal lock. Chemical shifts are reported relative to tetramethylsilane.

109

Cyclohexane, 0.185 M in deuterated solvent (100 L in 5.00 mL of solvent), was used as an internal standard for concentration determination. Tris(acetylacetonato)chromium(III) was used in small amounts in the deuterated solvent as a relaxation agent for NMR analysis. Pyridine derivative complexes of [(CH3CN)4Cu]PF6 were synthesized in situ before treatment with olefins.

Synthesis of [(CH3CN)4Cu]PF6

Tetrakisacetonitrile copper(I) hexafluorophosphate was synthesized using a modification of literature procedures.168 Cuprous oxide (4.02 g, 27.9 mmol) was suspended in 80 mL of acetonitrile. To this, 10 mL of 60% HPF6 (6.00 g, 41.1 mmol) was added dropwise, resulting in heat release and initially a pale red solution that turned yellow with a small amount of black solid. The solution was filtered hot, and diethyl ether (90 mL) was added to the filtrate, resulting in a cloudy white mixture.

[(MeCN)4Cu]PF6 was collected by vacuum filtration and washed with diethyl ether (3

15 mL). The resulting white solid was then dissolved in a minimal volume of acetonitrile and stored at 10 °C for 12 h. The resulting white crystals were isolated by vacuum

1 filtration and dried in vacuo. Yield: 8.35 g, 17.8 mmol, 82%. H NMR (acetone-d6, 200

168 MHz): δ 2.29 (s, 12 H). Mp 161 °C (dec; lit. 160 °C).

Preparation of [(Me-nic)3Cu(C2H4)]PF6

A 0.288 M solution of [(CH3CN)4Cu]PF6 was prepared by dissolving

[(CH3CN)4Cu]PF6 (0.473 g, 1.27 mmol) in acetone (4.40 mL). Methyl nicotinate (0.293 g, 2.14 mmol) was dissolved in acetone (2.50 mL), creating a 0.855 M solution. Five

110

NMR scale samples were prepared from these stock solutions using 500 L of

[(CH3CN)4Cu]PF6 solution and 520 L of methyl nicotinate solution. Volatiles were removed in vacuo, resulting in a yellow residue, which was then dissolved in acetone-d6 or CDCl3 (800 L). A stream of C2H4 was bubbled through the solution for 10 to 50 s in

1 increments of 10 s. H NMR (acetone-d6, 600 MHz): 9.43 (s, broad, 3H, ortho-H), 9.21

(s, broad, 3H, ortho-H), 8.57 (s, broad, 3H, para-H) 7.95 (s, broad, 3H, meta-H), 4.89 (s,

4H, C2H4), 3.95 (s, 9H, CH3, methyl nicotinate), 2.21 (s, 3H, CH3, CH3CN), 1.42 (s, 12H,

1 cyclohexane). H NMR (CDCl3, 400 MHz): 9.08 (s, broad, 3H, ortho-H), 8.78 (s, broad, 3H, ortho-H), 8.43 (s, broad, 3H, para-H) 7.62 (s, broad, 3H, meta-H), 4.98 (s,

4H, C2H4), 3.95 (s, 9H, CH3, methyl nicotinate), 2.16 (s, 3H, CH3CN), 1.40 (s, cyclohexane).

Preparation of [(Me-nic)3Cu(C3H6)]PF6

A 0.288 M solution of [(CH3CN)4Cu]PF6 was prepared by dissolving

[(CH3CN)4Cu]PF6 (0.473 g, 1.27 mmol) in acetone (4.40 mL). Methyl nicotinate (0.293 g, 2.14 mmol) was dissolved in acetone (2.50 mL), creating a 0.855 M solution. Six

NMR scale samples were prepared from these stock solutions using 500 L of

[(CH3CN)4Cu]PF6 solution and 520 L of methyl nicotinate solution. Volatiles were removed in vacuo, resulting in a yellow residue, which was then dissolved in acetone-d6 or CDCl3 (800 L). A stream of C3H6 was bubbled through the solution for 10 to 60 s in

1 10 s increments. H NMR (CDCl3, 600 MHz): 9.02 (s, broad, 3H, ortho-H), 8.71 (s, broad, 3H, ortho-H), 8.37 (s, broad, 3H, para-H), 7.57 (s, broad, 3H, meta-H), 5.68 (m,

1H, internal H, propylene), 4.85 (d, 1H, cis-H), 4.80 (d, 1H, trans-H), 3.89 (s, 9H, CH3,

111 methyl nicotinate), 2.13 (s, 3H, CH3CN), 1.63 (d, 3H, CH3, propylene), 1.42 (s, cyclohexane).

Preparation of [(3-(MeO)py)3Cu(C2H4)]PF6

A 0.333 M solution of [(CH3CN)4Cu]PF6 was prepared by dissolving

[(CH3CN)4Cu]PF6 (0.494 g, 1.33 mmol) in acetone (4.00 mL). 3-Methoxypyridine

(0.398 g, 0.370 mL, 3.65 mmol) was dissolved in acetone (4.00 mL), creating a 0.913 M solution. Four NMR scale samples were prepared from these stock solutions using 450

L of [(CH3CN)4Cu]PF6 solution and 490 L of 3-methoxypyridine solution. Volatiles were removed in vacuo, resulting in a yellow residue, which was then dissolved in acetone-d6 or chloroform-d (800 L). A stream of C2H4 was bubbled through the

1 solution for 10 to 40 s. H NMR (acetone-d6, 600 MHz): 8.41 (s, broad, 3H, ortho-H),

8.38 (s, broad, 3H, ortho-H), 7.66 (d, 3H, para-H), 7.59 (s, broad, 3H, meta-H), 4.84 (s,

4H, C2H4), 3.92 (s, 9H, CH3, 3-methoxypyridine), 2.14 (s, 3H, CH3CN), 1.42 (s,

13 1 cyclohexane). C{ H} NMR (acetone-d6, 100 MHz): 142.9 (ortho-C), 139.0 (ortho-

C), 122.9 (para-C), 117.8 (meta-C), 110.8 (ethylene), 56.4 (methoxy).

Reaction of [(Me-nic)3Cu(NCCH3)]PF6 and 1-hexene

A 0.294 M solution of [(CH3CN)4Cu]PF6 was prepared by dissolving

[(CH3CN)4Cu]PF6 (0.274 g, 0.735 mmol) in acetone (2.50 mL). Methyl nicotinate (0.292 g, 2.13 mmol) was dissolved in acetone (2.50 mL) creating a 0.852 M solution. Five

NMR scale samples were prepared from these stock solutions using 500 L of

[(CH3CN)4Cu]PF6 solution and 520 L of methyl nicotinate solution. Volatiles were

112 removed in vacuo, resulting in a yellow residue, which was then dissolved in acetone-d6

(800 L). 1-hexene (10 L, 0.08 mmol) was added to the solutions via syringe. 1H

NMR (acetone-d6, 600 MHz): 9.38 (s, broad, 6H, ortho-H), 8.54 (m, broad, 3H, para-

H), 7.88 (s, broad, 3H, meta-H), 5.78 (m, 1H, CH, internal olefinic H), 4.95 (d, 1H, CH, cis-olefinic H), 4.88 (d, 1H, CH, trans-olefinic H), 3.95 (s, 9H, CH3, methyl nicotinate),

2.15 (s, 3H, CH3, CH3CN), 2.04 (m, 2H, CH2, hexene), 1.42 (s, cyclohexane), 1.33 (m,

2H, CH2, hexene), 0.88 (t, 3H, CH3, hexene).

Reaction of [(Me-nic)3Cu(NCCH3)]PF6 and trans-3-hexene

A 0.294 M solution of [(CH3CN)4Cu]PF6 was prepared by dissolving

[(CH3CN)4Cu]PF6 (0.274 g, 0.735 mmol) in acetone (2.50 mL). Methyl nicotinate (0.292 g, 2.13 mmol) was dissolved in acetone (2.50 mL), creating a 0.852 M solution. Five

NMR scale samples were prepared from these stock solutions using 500 L of

[(CH3CN)4Cu]PF6 solution and 520 L of methyl nicotinate solution. Volatiles were removed in vacuo, resulting in a yellow residue, which was then dissolved in acetone-d6

(800 L). Trans-3-hexene (10 L, 0.08 mmol) was added to the solutions via syringe.

1 H NMR (acetone-d6, 600 MHz): 9.38 (s, broad, 6H, ortho-H), 8.54 (s, broad, 3H, para-H), 7.88 (s, broad, 3H), 5.43 (t, 2H, CH, olefinic), 1.97 (m, 4H, CH2, hexene), 2.16

(s, 3H, CH3CN), 1.42 (s, cyclohexane) 0.94 (t, CH3, hexene).

Reaction of [(Me-nic)3Cu(NCCH3)]PF6 and cis-3-hexene

A 0.294 M solution of [(CH3CN)4Cu]PF6 was prepared by dissolving

[(CH3CN)4Cu]PF6 (0.274 g, 0.735 mmol) in acetone (2.50 mL). Methyl nicotinate (0.292

113 g, 2.13 mmol) was dissolved in acetone (2.50 mL) creating a 0.852 M solution. Five

NMR scale samples were prepared from these stock solutions using 500 L of

[(CH3CN)4Cu]PF6 solution and 520 L of methyl nicotinate solution. Cis-3-hexene (10

1 L, 0.08 mmol) was added to these solutions via syringe. H NMR (acetone-d6, 600

MHz): 9.48 (s, broad, 6H, ortho-H), 8.55 (s, broad, 3H, para-H), 7.96 (s, broad, 3H, meta-H), 5.31 (t, 2H, CH, olefinic), 3.94 (s, 9H, CH3, nicotinate), 2.15 (s, 3H, CH3CN),

2.03 (m, 4H, CH2, hexene), 1.42 (s, cyclohexane), 0.93 (t, 6H, CH3, hexene).

Methods of Data Collection and Calculations

Variable temperature (VT) NMR spectroscopy is typically used to determine certain variables for calculations involving kinetic and thermodynamic studies of fluxional systems. Often, VT NMR is used to determine the coalescence temperature

(Tc) of a system in order to calculate kinetics values such as the rate of exchange k, and thermodynamic values such as G‡, H‡, and S‡. When the system is below the coalescence temperature, a separation of the resonances (in Hz) can be used to calculate the exchange rate from the NMR spectra (eq. 4.1).169

π 2 2 k o ΔνΔν (4.1) 2

o: separation when exchange rate is negligible, : observed separation

The copper(I)-olefin complexes were analyzed using VT NMR spectroscopy. The system‟s temperature was decreased in 10 C increments, and the broad resonance for ethylene remained unchanged down to 80 C; these systems never revealed a coalescence temperature. This suggests that even at extremely low temperatures, these

114 systems are still fluxional in solution and exchange remains rapid on the NMR timescale.

Consequently, separation of the two olefinic positions could not be determined, and an extrapolation method was used to determine the “bound” shift position of ethylene in the system, which allowed for equilibrium constant determination.

Extrapolation of a linear analysis plot of ethylene concentration, [C2H4] and NMR peak shift, , in ppm was used for the bound shift position of ethylene. Extrapolation to where [C2H4] is “zero” allows for calculation of where the bound shift for ethylene should appear (Figure 4.3). This extrapolation allows for equilibrium constants of the system to be obtained from the y-intercept of the plot.

[C2H4] vs. C2H4 Shift y = 0.9799x + 4.8652 R2 = 0.9262 5.100

5.050

5.000

, ppm 4.950

4.900

4.850 0.0000 0.0500 0.1000 0.1500 0.2000

[C2H4], mol/L

Figure 4.3. A linear plot of [C2H4] versus chemical shift in the presence of complex

77. Extrapolation to a [C2H4] of “zero” allows for the shift determination

of 4.865 ppm for bound C2H4. Data obtained in acetone-d6.

Equilibrium constants for ethylene binding can be obtained from 1H NMR data.

Consider the following equilibrium:

115

[(Me-nic)3Cu(CH3CN)]PF6 + C2H4 [(Me-nic)3Cu(C2H4)]PF6 + CH3CN

The equilibrium constant of this system can be calculated using the following equation:

Me nic 3 Cu()[{( HC PF ][)} 3642 CNCH ] K eq (4.2) Me nic 3 ()[{( 3CNCHCu PF ][)} HC 426 ]

The concentration of ethylene and tris(methyl nicotinate)copper(I) acetonitile hexafluorophosphate can be found by taking the area of the corresponding peaks in the

1H NMR spectrum, divided by the number of protons represented by that peak, multiplied by the known concentration of the internal standard, for example:

AreaPeak HC ][ [ StdInternal ] (4.3) 42 # of protons

The fractions of free and bound olefin can be determined using the calculated

“bound” peak position. The observed shift ( obs) in the NMR spectrum for the olefinic protons is a weighted average of chemical shifts for free ( f) and bound ( b) olefin in the system at fast exchange. This weighted fraction is related to the peak position using

Equation 4.4:

obs f b xx )1()( (4.4)

116

This equation can be rearranged and variables can be substituted to calculate the concentration of the copper-olefin complex:

fobs )( [{Me nic 3 Cu() HC )}PF642 HC 42 ][] (4.5) (1( bf ))

The equilibrium constant can be obtained from Equation 4.2 using the concentrations of products and reactants calculated by Equations 4.3, 4.4, and 4.5.

4.3 Results and Discussion

4.3.1 In-situ generation of copper-olefin complexes

Several nitrogen donor ligands and pyridine derivatives have been explored for their use in copper(I)-olefin transport systems by the Averill group. NMR scale reactions of pyridine derivatives 72, 73, and 74 with [(CH3CN)4Cu]PF6 yielded complexes 75, 76,

77 of the form [L3Cu(NCCH3)]PF6, respectively. After removal of volatiles and three equivalents of acetonitrile in vacuo, the remaining residue was dissolved in deuterated

NMR solvent containing Cr(acac)3 (10 mol%). Alkene was added to the sample by either bubbling ethylene gas through the solution for standard amounts of time or adding liquid samples via microsyringe, and sealed in J-Young NMR tubes under nitrogen pressure.

117

CH3 C

N H2C CH2

Cu H2C CH2 Cu

N N - CH3CN N N N N

R R R R R R R = CO2CH3, OCH3, OH

Acetone-d6 and CDCl3 were used as solvents in this study to compare the active role of a coordinating and non-coordinating solvent, respectively, in these transport systems. For industrial applications, the solvent can play an important part in olefin complex formation for olefin separation. A coordinating solvent (acetone) will compete for binding to the copper(I) complex, and the olefin will bind less preferentially, which will lower the equilibrium constant (Keq) value. A non-coordinating solvent (chloroform) will not compete for coordination to the metal center, allowing olefins to access the metal center, and therefore, Keq is expected to be higher.

4.3.2 Olefin Binding Studies

[(Me-nic)3Cu(C2H4)]PF6 in acetone-d6

118 binding to the copper center. At 20 °C, the equilibrium constant was calculated to be

3.77 ± 0.85. At 45 °C, the equilibrium constant was calculated to be 4.82 ± 1.41, suggesting that at higher temperature, no distinct difference is observed. At 5 °C, Keq was calculated to be 4.31 ± 1.38.

[(Me-nic)3Cu(C2H4)]PF6 in CDCl3

Proton chemical shifts for bound ethylene shifted upfield relative to those for free ethylene. The olefin system is in rapid exchange at temperatures down to 80 °C, and peak separation of bound and free ethylene resonances was not observed. A plot of ethylene concentration versus the weighted average chemical shift of the olefin revealed a bound shift position of 4.887 ppm, 0.52 ppm upfield of free ethylene. At 20 °C, the equilibrium constant for this system was calculated to be 4.50 ± 0.51. At 45 °C, the equilibrium constant could not be calculated due to decomposition at temperatures greater than 35 °C. This suggests that these types of complexes are not thermally stable in halogenated solvents. At 5 °C, however, the complexes were stable, and Keq was calculated to be 6.24 ± 0.68.

[(Me-nic)3Cu(C3H6)]PF6 in CDCl3

Proton chemical shifts for bound propylene shifted upfield relative to those for free propylene. Cooling of the system to 80 °C revealed that the system was still in rapid exchange at low temperatures, and separation of propylene resonances was not observed. A plot of propylene concentration versus the weighted average chemical shift of the olefin revealed a bound shift position of 5.63 ppm for the internal olefinic proton.

119

This shift is 0.21 ppm upfield of free propylene. At room temperature, this system is in rapid exchange. At 20 °C, the equilibrium constant for this system was calculated to be

4.06 ± 3.12. A high error is associated with this value, which may be attributed to instability of this complex in the deuterated solvent. At 45 °C, the equilibrium constant could not be calculated due to decomposition at temperatures greater than 35 °C, and therefore data could not be obtained. This suggests that these types of complexes are not thermally stable in halogenated solvents. At 5 °C, however, the complexes were stable, and Keq was calculated to be 1.91 ± 1.01.

Binding of 1-hexene to [(Me-nic)3Cu(NCCH3)]PF6 in acetone-d6

Chemical shifts for olefinic protons exhibited essentially no change from those of free 1-hexene resonances, indicating a lack of 1-hexene binding to the metal complex.

Olefinic proton resonances appeared at 5.78 ppm and 4.95 ppm, both upfield shifts from free olefin in solution of 0.01 ppm and 0.04 ppm, respectively. This minimal chemical shift change was seen even in concentrations lower than one olefin equivalent. Variation in the number of methyl nicotinate ligands around the copper(I) center also resulted in no change in olefinic proton chemical shift. Complexes with one, two, and three methyl nicotinate ligands were prepared in situ via stock solutions, and no chemical shift change was observed.

Binding of cis-3-hexene to [(Me-nic)3Cu(NCCH3)]PF6 in acetone-d6

Chemical shifts for olefinic protons exhibited no change from those of free cis-3- hexene, indicating a lack of cis-3-hexene binding to the metal complex. Olefinic proton

120 resonances appeared at 5.31 ppm, with no shift from free olefin (5.31 ppm) in solution.

This lack of chemical shift change was observed even in concentrations lower than one olefin equivalent.

Binding of trans-3-hexene to [(Me-nic)3Cu(NCCH3)]PF6 in acetone-d6

Chemical shifts for olefinic protons exhibited no change from those of free trans-

3-hexene, indicating a lack of trans-3-hexene binding in this complex. Olefinic proton resonances appeared at 5.43 ppm, with no shift from the free olefin shift of 5.43 ppm in solution. This lack of chemical shift change was observed even at concentrations lower than one olefin equivalent.

[(3-MeOpy)3Cu(C2H4)]PF6 in acetone-d6

Proton chemical shifts for bound ethylene shifted upfield relative to those for free ethylene. The olefin system was in rapid exchange at temperatures down to 80 °C, and peak separation of bound and free ethylene resonances was not observed. A plot of ethylene concentration versus the weighted average chemical shift of the olefin revealed a bound shift position of 4.74 ppm, 0.64 ppm upfield from free ethylene. At 20 °C, the equilibrium constant was calculated to be 3.50 ± 0.44. Variable temperature spectra were not collected for [(3-MeOpy)3Cu(C2H4)]PF6 as decomposition was observed at 45 °C.

Analysis at 5 °C did not reveal a significant difference from values obtained at room temperature.

121

Binding of 1-hexene to [(3-HOpy)3Cu(NCCH3)]PF6 in acetone-d6

Chemical shifts of olefinic protons exhibited essentially no change from those of free 1-hexene, indicating a lack of 1-hexene binding in this complex. Olefinic proton resonances appeared at 5.75 ppm and 4.92 ppm, both upfield shifts of 0.04 ppm and 0.07 ppm, respectively, from free olefin in solution. This minimal chemical shift change was seen even in concentrations lower than one olefin equivalent. Variation in the number of

3-hydroxypyridine ligands around the copper(I) center also resulted in minimal change in olefinic proton chemical shift. Complexes with one, two, and three 3-hydroxypyridine ligands were prepared in situ via stock solutions, and no chemical shift change was observed.

[(py)xCu(NCCH3)4-x]PF6 (78) with 1-hexene or cis-3-hexene in acetone-d6

To compare results to the work by J.C. Davis with the copper(I) pyridine systems, copper(I) complexes with one, two, or three pyridine ligands were prepared in situ.

These systems were allowed to react with 1-hexene and cis-3-hexene to study their ability to bind larger olefins. In the presence of three pyridine ligands, the 1-hexene olefinic protons exhibited resonances at 5.79 ppm and 4.99 ppm, indicating no shift change from free olefin. In the presence of two pyridine ligands, minimal changes in the olefinic proton shifts was observed at 5.77 ppm and 4.97 ppm, a change of 0.02 ppm in both cases. In the presence of one pyridine ligand, olefinic protons exhibited minimal change again, with shifts of 5.76 ppm and 4.93 ppm, a change of 0.03 ppm and 0.06 ppm respectively. Studies of olefin binding with cis-3-hexene produced results similar to those with 1-hexene. In the presence of three pyridine ligands, the olefinic proton shifts

122

of cis-3-hexene did not change from 5.31 ppm. Only minimal shifts were observed in the

presence of two pyridine ligands resulting in an olefinic proton shift of 5.30 ppm, a 0.01

ppm change.

[(CH3CN)4Cu]PF6 (79) with C2H4, 1-hexene, or cis-3-hexene in acetone-d6

As a control experiment, olefin binding studies were performed with the copper(I)

precursor [(CH3CN)4Cu]PF6 and ethylene, 1-hexene, and cis-3-hexene. The olefinic

protons of ethylene in the presence of [(CH3CN)4Cu]PF6 resulted in an upfield shift of

0.29 ppm to 5.09 ppm. The olefinic protons of 1-hexene in the presence of

[(CH3CN)4Cu]PF6 show minimal upfield shifts of 0.01 ppm and 0.04 ppm to 5.78 ppm

and 4.95 ppm, repectively. Chemical shift changes for cis-3-hexene were similar to those

of 1-hexene. An upfield shift of 0.01 ppm to 5.30 ppm was observed for cis-3-hexene.

Table 4.1. Summary of equilibrium constants (K) at 20 °C.

69 70 71 75 76 77 ethylene 5.8 0.85 4.6 3.5 not tested 3.8, 4.5* propylene 0.78 - - - not tested 4.1* 1-hexene 0.47 0.75 4.9 - - - -3 cis-3-hexene 7.2 10 0.69 13 - - - -4 trans-3-hexene 4.3 10 - 1.8 - - - *Calculated in CDCl , all other values in acetone-d 3 6

123

Table 4.2. Summary of olefinic proton chemical shift changes at 20 °C (ppm).

75 76 77 78 79 ethylene 0.64 - 0.52, 0.52* - 0.70 propylene - - 0.21* - -

1-hexene - 0.04 0.01 0.02** 0.01 cis-3-hexene - - 0.00 0.01** 0.01 trans-3-hexene - - 0.00 - - *Data in CDCl3. **Average of data with 3 to 1 pyridine ligands.

Table 4.3. Summary of variable temperature equilibrium constants for ethylene binding.

-5 °C 20 °C 45 °C

acetone-d6 4.31 3.77 4.82

CDCl3 6.24 4.50 decomp Data shown represents C2H4 in the presence of 77.

From these results, it can be concluded that complexes 75 and 77 do not bind

ethylene as well as complexes with tridentate nitrogen donor ligands (69, 71). This may

be attributed to competition for -backbonding from the copper center to the pyridine

ligands, thus leading to lower Keq values. Binding studies of 75 resulted in a Keq for

ethylene comparatively lower than those of complex 69 and 71. However, complex 75

exhibits an approximate four-fold larger Keq than complex 70. Binding studies of 77

resulted in a binding order of ethylene > propylene. Larger terminal olefins and internal

olefins such as 1-hexene, cis-3-hexene, and trans-3-hexene did not bind. This leads to

the conclusion that 77 binds olefins relatively weakly; the drastic decrease in affinity for

larger olefins is not unexpected, as the same trend is seen in complex 69. Thus, with a

lower Keq for ethylene comparative to complex 69, and a ~10 fold decrease from ethylene

124 to 1-hexene in complex 69, larger olefins are not expected to bind to complex 77.

Binding studies of complex 76 were hindered, as preparation of these complexes in situ resulted in decomposition to a white solid in solution. It should be noted, however, that some stable samples were obtained, but minimal shifts of the olefinic protons of 1-hexene were observed. This indicates that complex 76 does not bind larger terminal olefins, not an unexpected observation, inasmuch as this trend is seen in complexes 75, 76, 77, 78, and 79.

Olefin binding studies of pyridine derivative copper(I) complexes revealed that even at temperatures as low as 80 °C, the slow exchange limit is not reached.

Therefore, variable temperature studies were performed for complex 77 at temperatures of 45 °C, 20 °C and 5 °C. As summarized in Table 4.3, studies of this system at these temperatures were inconclusive. Equilibrium constant values were higher at 5 °C and

45 °C than at 20 °C in acetone-d6, resulting in no definite correlation between Keq and temperature. This study was further expanded by testing complex 77 with ethylene in

CDCl3 at 5 °C, 20 °C, and 45 °C. This study revealed that complex 77 decomposes at

45 °C and data could not be obtained. However, Keq is higher at 5 °C than at 20 °C; a similar trend is seen in acetone-d6. It should be noted that equilibrium constants were higher in CDCl3 than in acetone-d6. This result is expected, as CDCl3 cannot compete for a coordination site of the metal center, therefore increasing the ability for complex 77 to bind ethylene.

125

4.4 Conclusions

Three copper(I) complexes (75, 76, 77) were prepared in situ using pyridine derivative ligands. All three derivatives are presumed to be very similar in structure, but their electronic properties should differ. Complexes 75, 76, and 77 displayed lower affinity for olefins compared to copper(I) complexes with pentamethyldiethylenetriamine ligands. Complex 75 displayed an affinity for ethylene, although Keq was slightly lower than that of complex 77. Complex 76 did not appear to bind larger olefins. It was difficult to prepare and study due to fast decomposition, and it was therefore not studied extensively. Complex 77 had the greatest affinity for olefins compared to 75 and 76.

Complexes 75, 76, and 77 do not appear to bind larger or terminal olefins. Variable temperature studies of complex 77 revealed no distinct correlation between binding constants and temperature in this system. Studies of the role of coordinating and non- coordinating solvents in olefin binding have shown that complex 77 exhibits a higher binding constant in a non-coordinating solvent than in a coordinating solvent. Pyridine derivative complexes do show an affinity for smaller olefins such as ethylene and propylene, but do not show any affinity for larger olefins. These types of complexes may be useful in industrial olefin separations.

126

Chapter 5

Concluding Remarks

This dissertation reports research conducted in three distinct areas. First, the synthesis and characterization of indolyl- and pyrrolyl-based constrained geometry ligands, and the reactivity of the indolyl-based ligands with group 4 and 5 transition metals was investigated. A closely related set of titanium-imido complexes were prepared using di(3-methylindolyl)methane ligands. These studies were performed as the initial preparation of indole-based CGCs in hopes to generate electrophilic metal complexes. Second, the binding affinities of copper-pyridine complexes with alkenes were also investigated in order to investigate their separation capabilities in a mixture of alkenes. Finally, the preparation of aluminum and gallium metallophosphinates and metallophosphonates was also investigated (Appendix 1). This study was performed in hopes to generate molecular building blocks to serve in the preparation of porous three- dimensional frameworks.

Chapter 2 describes the preparation of fluorenyl, indenyl, and cyclopentadienyl acetals as well as their condensation products in the formation of indole- and pyrrole- based constrained geometry ligands. These compounds, namely fluorenyl acetaldehyde diethylacetal (48), indenyl acetaldehyde diethylacetal (49), and cyclopentadienyl acetaldehyde diethylacetal (50), serve as precursors to di(3-methylindolyl)- and

127 dipyrrolyl-ethanes. Fluorenyl di(3-methylindolyl)ethane (51), fluorenyl dipyrrolylethane

(52), indenyl di(3-methylindolyl)ethane (53), and indenyl dipyrrolylethane (54) were successfully synthesized and characterized by NMR spectroscopy, mass spectrometry, and X-ray crystallography. The preparation of the di(3-methylindolyl)ethanes is reproducible in high to moderate yields, but the preparation of dipyrrolylethanes is less straightforward and proceeds in low yields. This is attributed to the formation of pyrrole compounds substituted in the 2- and 5-positions of the pyrrole ring, as well as the formation of N-confused products.

Chapter 3 describes the synthesis and spectroscopic characterization of a series of bidentate, constrained geometry, and related metal complexes. Within this report are examples of bidentate di(3-methylindolyl)ethanes, specifically in the formation of

(HFDI)Zr(NEt2)2(THF) (58) and (HFDI)Ti(NEt2)2 (59). Complexes 58 and 59 are structurally analogous to previously reported di(3-methylindolyl)methane complexes.

These complexes were synthesized via amine elimination reactions and were characterized by NMR spectroscopy. Complex 58 was also characterized by X-ray crystallography. Several methods were attempted to drive deprotonation the fluorenyl proton of 58 via amine elimination, however the low acidity of this proton and steric congestion hinders 5-coordination to the metal center via amine elimination. Also within this report is the synthesis and characterization of a constrained geometry complex

(IDI)Zr(NEt2) (60), which was formed via amine elimination. This complex was characterized by NMR spectroscopy and X-ray crystallography. X-ray structural analysis confirmed 5-coordination of the indenyl moiety to the zirconium center, as well as the asymmetrical structure of 60. This complex is the first reported example of a CGC with a

128 trianionic di(3-methylindolyl)ethane ligand. Also reported in this chapter is the formation of zirconium and titanium CGCs via salt metathesis reactions. Specifically,

(FDI)M(CH3) (M = Zr (61), Ti (62)) was prepared via reaction of H3FDI and the appropriate metal chloride in the presence of four equivalents of methyllithium. These complexes were characterized by NMR spectroscopic methods. The preparation of 61 was reproducible and proceeded in moderate yields, but the preparation of 62 was not as reproducible and proceeded in low yield. These complexes represent the first reported methyl complexes with di(3-methylindolyl)ethane ligands. The formation of constrained geometry niobium-imido complexes, specifically (IDI)Nb(NtBu)(py) (63) and

(IDI)Nb(NPh) (64) are reported. These complexes were prepared via salt metathesis reactions of H3IDI and niobium-imido reagents. The preparation of 63 was reproducible and worked in high yields, but the preparation of 64 was more sensitive and worked in low yield. Also reported was the synthesis and characterization of a series of titanium- imido complexes with di(3-methylindolyl)methanes. These complexes were prepared through salt metathesis reactions of the di(3-methylindolyl)methanes and titanium-imido reagents. Specifically, (tBuN)Ti{(2-pyridyl)di(3-methylindolyl)methane} (65),

(tBuN)Ti{(2-methoxyphenyl)di(3-methylindolyl)methane} (66), and (tBuN)Ti{(N- methylimidazolyl)di(3-methylindolyl)methane} (67) were prepared. Complexes 65, 66, and 67 were characterized by NMR spectroscopy. Incomplete X-ray characterization of

65 confirmed the connectivity of this complex. Complexes 65 and 66 were prepared in moderate yields as microcrystalline materials, and complex 67 was prepared in low yield as a microcrystalline material. Repeated attempts to obtain crystals suitable for X-ray

129 structural analysis were unsuccessful. These complexes represent the intial study of group 4 imido complexes using the di(3-methylindolyl)methane framework.

Chapter 4 discusses a study of the binding affinity of copper(I)-pyridine complexes with alkenes. Within this report is the in situ generation of [(3-

MeOpy)3Cu(NCCH3)]PF6 (75), [(3-HOpy)3Cu(NCCH3)]PF6 (76), and [(Me- nic)3Cu(NCCH3)]PF6 (77). Binding affinities of complexes 75 and 77 were studied with ethylene, propylene, 1-hexene, cis-3-hexene, and trans-3-hexene. Complex 77 exhibited a higher binding affinity for ethylene and propylene than complex 75. Both 75 and 77 did not bind 1-hexene, cis-3-hexene, or trans-3-hexene. Complex 76 exhibited rapid decomposition upon preparation, which hindered binding studies. Although complexes

75 and 77 exhibited binding affinities for ethylene and propylene, Keq values were considerably lower than those of copper(I) complexes with neutral, chelating amine ligands.

Appendix 1 discusses the initial studies in the preparation of alumino- and gallophosphinate 4R structures from reaction of triphenylaluminum and triphenylgallium with diphenylphosphinic acid. Specifically, [Ph2AlO2PPh2]2 (A), [Ph2GaO2PPh2]2 (B),

[Ph2AlO2P(OPh)2]2 (C), and [Ph2GaO2P(OPh)2]2 (D) were prepared. Compounds A-D were characterized by 1H and 31P NMR spectroscopy, and the connectivity of compound

A was characterized by X-ray crystallography. These compounds are a representative series of 4R structures with diphenylaluminum and diphenylgallium moieties. This study was performed in an effort to produce complexes that could potentially be linked in a porous three-dimensional array. Several attempts were made to produce D4R structures from reactions of triphenylaluminum and triphenylgallium with alkyl and arylphosphonic

130 acids. These attempts resulted in the formation of insoluble materials that were difficult to characterize using traditional methods.

In future research, several complexes of group 4-6 transition metals should be prepared using the di(3-methylindolyl)- and dipyrrolylethane constrained geometry frameworks. Optimization should be performed on the preparation of the dipyrrolyl ligands in hopes to increase isolated yield. Methods other than those attempted in chapter

2 should be explored to generate cyclopentadienyl di(3-methylindolyl)- and dipyrrolylethanes. This type of ligand could make the formation of metal complexes more straightforward. Furthermore, group 5 metals with the fluorenyl, indenyl, and cyclopentadienyl ligand sets should be explored for their potential use as alkene polymerization and copolymerization catalysts. Catalytic activity as well as polydispersity index should be analyzed. Generation of dialkyl group 5 metal complexes should be attempted, as well as the generation of cationic species of these complexes via alkide abstraction agents. Also, group 4 and 5 metal-imido complexes should be explored for their potential use as alkene hydroamination catalysts.

131

References

1. Cano, J.; Kunz, K. J. Organomet. Chem. 2007, 692, 4411-4423.

2. Stevens, J. C.; Timmers, F. J.; Wilson, D. R.; Schmidt, G. F.; Nikias, P. N.;

Rosen, R. K.; Knight, G. W.; Lai, S. Constrained Geometry Addition

Polymerization Catalysts, Processes for their Preparation, Precursors Therefore,

Methods of Use, and Novel Polymers Formed Therewith. EP-416815-A2, August

30, 1990.

3. Shapiro, P. J.; Bunel, E.; Schaefer, W. P.; Bercaw, J. E. Organometallics 1990, 9,

867-869.

4. Okuda, J. Chem. Ber. 1990, 123, 1649-1651.

5. Braunschweig, H.; Breitling, F. M. Coord. Chem. Rev. 2006, 250, 2691-2720.

6. Cotton, F. A.; Wilkinson, G.; Murillo, C. A.; Bochmann, M. Advanced Inorganic

Chemistry; Sixth ed.; John Wiley & Sons, Inc.: New York, 1999.

7. Ziegler, K.; Holzkamp, E.; Breil, H.; Martin, H. Angew. Chem. 1955, 67, 541.

8. Ziegler, K. Angew. Chem. 1964, 76, 545.

9. Natta, G. Angew. Chem. 1956, 68, 393-404.

10. Natta, G. Angew. Chem. 1964, 76, 553.

11. Hogan, J. P.; Banks, R. L. Polymerization of olefins. US002825721, 1958.

12. Karapinka, G. L. Bis(cyclopentadienyl)chromium-catalyzed ethylene

polymerization. DE1808388 19700129, 1970.

132

13. Weckhuysen, B. M.; Schoonheydt, R. A. Catal. Today 1999, 51, 215-221.

14. Cossee, P. J. Catal. 1964, 3, 80-88.

15. Arlman, E. J. J. Catal. 1964, 3, 89-98.

16. Arlman, E. J.; Cossee, P. J. Catal. 1964, 3, 99-104.

17. Bochmann, M. J. Chem. Soc. Dalton Trans. 1996, 255-270.

18. Brintzinger, H. H.; Fischer, D.; Mulhaupt, R.; Rieger, B.; Waymouth, R. M.

Angew. Chem. Int. Ed. 1995, 34, 1143-1170.

19. Kaminsky, W.; Arndt, M. Adv. Polym. Sci. 1997, 127, 143-187.

20. Schneider, N.; Huttenloch, M. E.; Stehling, U.; Kirsten, R.; Schaper, F.;

Brintzinger, H. H. Organometallics 1997, 16, 3413-3420.

21. Wilson, P. A.; Wright, J. A.; Oganesyan, V. S.; Lancaster, S. J.; Bochmann, M.

Organometallics 2008, 27, 6371-6374.

22. Ittel, S. D.; Johnson, L. K.; Brookhart, M. Chem. Rev. 2000, 100, 1169-1203.

23. Killian, C. M.; Johnson, L. K.; Brookhart, M. Organometallics 1997, 16, 2005-

2007.

24. Johnson, L. K.; Killian, C. M.; Brookhart, M. J. Am. Chem. Soc. 1995, 117, 6414-

6415.

25. Laine, T. V.; Klinga, M.; Maaninen, A.; Aitola, E.; Leskela, M. Acta Chem.

Scand. 1999, 53, 968-973.

26. Gibson, V. C.; Spitzmesser, S. K. Chem. Rev. 2003, 103, 283-315.

27. Deng, L. Q.; Woo, T. K.; Cavallo, L.; Margl, P. M.; Ziegler, T. J. Am. Chem. Soc.

1997, 119, 6177-6186.

28. Chen, E. Y. X.; Marks, T. J. Chem. Rev. 2000, 100, 1391-1434.

133

29. Breslow, D. S.; Newburg, N. R. J. Am. Chem. Soc. 1957, 79, 5072-5073.

30. Sinn, H.; Kaminsky, W. Adv. Organomet. Chem. 1980, 18, 99-149.

31. Andersen, A.; Cordes, H. G.; Herwig, H.; Kaminsky, W.; Merk, A.; Mottweiler,

R.; Pein, J.; Sinn, H.; Vollmer, H. J. Angew. Chem. Int. Ed. Engl. 1976, 15, 630-

632.

32. Piers, W. E.; Chivers, T. Chem. Soc. Rev. 1997, 26, 345-354.

33. Yang, X. M.; Stern, C. L.; Marks, T. J. J. Am. Chem. Soc. 1991, 113, 3623-3625.

34. Krossing, I.; Raabe, I. Angew. Chem. Int. Ed. 2004, 43, 2066-2090.

35. Deck, P. A.; Beswick, C. L.; Marks, T. J. J. Am. Chem. Soc. 1998, 120, 1772-

1784.

36. Bijpost, E. A.; Duchateau, R.; Teuben, J. H. J. Mol. Catal. A. 1995, 95, 121-128.

37. Okuda, J.; Verch, S.; Sturmer, R.; Spaniol, T. P. J. Organomet. Chem. 2000, 605,

55-67.

38. Hussain, M.; Kohser, S.; Janssen, K.; Wartchow, R.; Butenschon, H.

Organometallics 2009, 28, 5212-5221.

39. Kunz, K.; Erker, G.; Doring, S.; Frohlich, R.; Kehr, G. J. Am. Chem. Soc. 2001,

123, 6181-6182.

40. Chen, Y. X.; Fu, P. F.; Stern, C. L.; Marks, T. J. Organometallics 1997, 16, 5958-

5963.

41. Seo, W. S.; Cho, Y. J.; Yoon, S. C.; Park, J. T.; Park, Y. J. Organomet. Chem.

2001, 640, 79-84.

42. Carpenetti, D. W.; Kloppenburg, L.; Kupec, J. T.; Petersen, J. L. Organometallics

1996, 15, 2668-2668.

134

43. Hughes, A. K.; Meetsma, A.; Teuben, J. H. Organometallics 1993, 12, 1936-

1945.

44. Herrmann, W. A.; Morawietz, M. J. A. J. Organomet. Chem. 1994, 482, 169-181.

45. Ashe, A. J.; Fang, X. G.; Kampf, J. W. Organometallics 1999, 18, 1363-1365.

46. Feng, S. G.; Klosin, J.; Kruper, W. J.; McAdon, M. H.; Neithamer, D. R.; Nickias,

P. N.; Patton, J. T.; Wilson, D. R.; Abboud, K. A.; Stern, C. L. Organometallics

1999, 18, 1159-1167.

47. Okuda, J.; Schattenmann, F. J.; Wocadlo, S.; Massa, W. Organometallics 1995,

14, 789-795.

48. Resconi, L.; Camurati, I.; Grandini, C.; Rinaldi, M.; Mascellani, N.; Traverso, O.

J. Organomet. Chem. 2002, 664, 5-26.

49. Chen, Y. X.; Marks, T. J. Organometallics 1997, 16, 3649-3657.

50. Gomes, P. T.; Green, M. L. H.; Martins, A. M.; Mountford, P. J. Organomet.

Chem. 1997, 541, 121-125.

51. Gomes, P. T.; Green, M. L. H.; Martins, A. M. J. Organomet. Chem. 1998, 551,

133-138.

52. Sinnema, P. J.; Loes van der Veen, L.; Spek, A. L.; Veldman, N.; Teuben, J. H.

Organometallics 1997, 16, 4245-4247.

53. Alt, H. G.; Fottinger, K.; Milius, W. J. Organomet. Chem. 1999, 572, 21-30.

54. Ciruelos, S.; Cuenca, T.; Gomez, R.; Gomez-Sal, P.; Manzanero, A.; Royo, P.

Organometallics 1996, 15, 5577-5585.

55. Ciruelos, S.; Cuenca, T.; Gomez-Sal, P.; Manzanero, A.; Royo, P.

Organometallics 1995, 14, 177-185.

135

56. Canich, J. A. M. Olefin Polymerization Catalysts. EP-420436-A1, September 10,

1990.

57. Bredeau, S.; Altenhoff, G.; Kunz, K.; Doring, S.; Grimme, S.; Kehr, G.; Erker, G.

Organometallics 2004, 23, 1836-1844.

58. Kotov, V. V.; Avtomonov, E. V.; Sundermeyer, J.; Harms, K.; Lemenovskii, D.

A. Eur. J. Inorg. Chem. 2002, 678-691.

59. Otero, A.; Fernandez-Baeza, J.; Antinolo, A.; Lara-Sanchez, A.; Martinez-

Caballero, E.; Tejeda, J.; Sanchez-Barba, L. F.; Alonso-Moreno, C.; Lopez-

Solera, I. Organometallics 2008, 27, 976-983.

60. Witte, P. T.; Meetsma, A.; Hessen, B.; Budzelaar, P. H. M. J. Am. Chem. Soc.

1997, 119, 10561-10562.

61. Witte, P. T.; Meetsma, A.; Hessen, B. Organometallics 1999, 18, 2944-2946.

62. Herrmann, W. A.; Baratta, W. J. Organomet. Chem. 1996, 506, 357-361.

63. Alcalde, M. I.; Gomez-Sal, M. P.; Royo, P. Organometallics 1999, 18, 546-554.

64. Gomez-Ruiz, S.; Hocher, T.; Prashar, S.; Hey-Hawkins, E. Organometallics 2005,

24, 2061-2064.

65. Arteaga-Muller, R.; Sanchez-Nieves, J.; Royo, P.; Mosquera, M. E. G.

Polyhedron 2005, 24, 1274-1279.

66. Liang, Y. F.; Yap, G. P. A.; Rheingold, A. L.; Theopold, K. H. Organometallics

1996, 15, 5284-5286.

67. Herrmann, W. A.; Baratta, W.; Morawietz, M. J. A. J. Organomet. Chem. 1995,

497, C4-C6.

68. Hughes, A. K.; Kingsley, A. J. J. Chem. Soc. Dalton Trans. 1997, 4139-4141.

136

69. Wang, T. F.; Lai, C. Y.; Hwu, C. C.; Wen, Y. S. Organometallics 1997, 16, 1218-

1223.

70. Wang, T. F.; Hwu, C. C.; Tsai, C. W.; Wen, Y. S. Organometallics 1998, 17, 131-

138.

71. Pietryga, J. M.; Gorden, J. D.; Macdonald, C. L. B.; Voigt, A.; Wiacek, R. J.;

Cowley, A. H. J. Am. Chem. Soc. 2001, 123, 7713-7714.

72. Pietryga, J. M.; Jones, J. N.; Mullins, L. A.; Wiacek, R. J.; Cowley, A. H. Chem.

Commun. 2003, 2072-2073.

73. Wiacek, R. J.; Macdonald, C. L. B.; Jones, J. N.; Pietryga, J. M.; Cowley, A. H.

Chem. Commun. 2003, 430-431.

74. Otero, A.; Fernandez-Baeza, J.; Antinolo, A.; Tejeda, J.; Lara-Sanchez, A.;

Sanchez-Barba, L.; Rodriguez, A. M.; Maestro, M. A. J. Am. Chem. Soc. 2004,

126, 1330-1331.

75. Cano, J.; Royo, P.; Lanfranchi, M.; Pellinghelli, M. A.; Tiripicchio, A. Angew.

Chem. Int. Ed. Engl. 2001, 40, 2495-2497.

76. Nugent, W. A.; Haymore, B. L. Coord. Chem. Rev. 1980, 31, 123-175.

77. Cundari, T. R. J. Am. Chem. Soc. 1992, 114, 7879-7888.

78. Benson, M. T.; Bryan, J. C.; Burrell, A. K.; Cundari, T. R. Inorg. Chem. 1995, 34,

2348-2355.

79. Mountford, P. Chem. Commun. 1997, 2127-2134.

80. Schaller, C. P.; Wolczanski, P. T. Inorg. Chem. 1993, 32, 131-144.

81. Dewith, J.; Horton, A. D. Angew. Chem. Int. Ed. Engl. 1993, 32, 903-905.

82. Wigley, D. E. Prog. Inorg. Chem. 1994, 42, 239.

137

83. Hill, J. E.; Profilet, R. D.; Fanwick, P. E.; Rothwell, I. P. Angew. Chem. Int. Ed.

Engl. 1990, 29, 664-665.

84. Roesky, H. W.; Voelker, H.; Witt, M.; Noltemeyer, M. Angew. Chem. Int. Ed.

Engl. 1990, 29, 669-670.

85. Sung, R. C. W.; Courtenay, S.; McGarvey, B. R.; Stephan, D. W. Inorg. Chem.

2000, 39, 2542-2546.

86. Dubberley, S. R.; Evans, S.; Boyd, C. L.; Mountford, P. Dalton Trans. 2005,

1448-1458.

87. Blake, A. J.; Collier, P. E.; Gade, L. H.; Mountford, P.; Lloyd, J.; Pugh, S. M.;

Schubart, M.; Skinner, M. E. G.; Trosch, D. J. M. Inorg. Chem. 2001, 40, 870-

877.

88. Gardner, J. D.; Robson, D. A.; Rees, L. H.; Mountford, P. Inorg. Chem. 2001, 40,

820-824.

89. Pugh, S. M.; Blake, A. J.; Gade, L. H.; Mountford, P. Inorg. Chem. 2001, 40,

3992-4001.

90. Ciszewski, J. T.; Harrison, J. F.; Odom, A. L. Inorg. Chem. 2004, 43, 3605-3617.

91. Fickes, M. G.; Odom, A. L.; Cummins, C. C. Chem. Commun. 1997, 1993-1994.

92. Agarwal, P.; Piro, N. A.; Meyer, K.; Muller, P.; Cummins, C. C. Angew. Chem.

Int. Ed. 2007, 46, 3111-3114.

93. Anderson, L. L.; Schmidt, J. A. R.; Arnold, J.; Bergman, R. G. Organometallics

2006, 25, 3394-3406.

94. Schmidt, J. A. R.; Arnold, J. Organometallics 2002, 21, 3426-3433.

138

95. Schmidt, J. A. R.; Giesbrecht, G. R.; Cui, C. M.; Arnold, J. Chem. Commun.

2003, 1025-1033.

96. Dunn, S. C.; Mountford, P.; Shishkin, O. V. Inorg. Chem. 1996, 35, 1006-1012.

97. Fletcher, J. S.; Male, N. A. H.; Wilson, P. J.; Rees, L. H.; Mountford, P.;

Schroder, M. J. Chem. Soc. Dalton Trans. 2000, 4130-4137.

98. Mason, M. R.; Fneich, B. N.; Kirschbaum, K. Inorg. Chem. 2003, 42, 6592-6594.

99. Cortright, S. B.; Coalter, J. N.; Pink, M.; Johnston, J. N. Organometallics 2004,

23, 5885-5888.

100. Mason, M. R.; Barnard, T. S.; Segla, M. F.; Xie, B. H.; Kirschbaum, K. J. Chem.

Crystallogr. 2003, 33, 531-540.

101. Mason, M. R.; Ogrin, D.; Fneich, B.; Barnard, T. S.; Kirschbaum, K. J.

Organomet. Chem. 2005, 690, 157-162.

102. Fneich, B. N. Ph.D. Dissertation, The University of Toledo, 2006.

103. Das, A. M.S. Thesis, The University of Toledo, 2007.

104. Sudupe, M.; Cano, J.; Royo, P.; Mosquera, M. E. G.; Frutos, L. M.; Castano, O.

Organometallics 2010, 29, 263-268.

105. Pi, C. F.; Zhang, Z. X.; Liu, R. T.; Weng, L. H.; Chen, Z. X.; Zhou, X. G.

Organometallics 2006, 25, 5165-5172.

106. Groux, L. F.; Zargarian, D. Organometallics 2003, 22, 3124-3133.

107. Tanski, J. M.; Parkin, G. Inorg. Chem. 2003, 42, 264-266.

108. Barnard, T. S.; Mason, M. R. Organometallics 2001, 20, 206-214.

109. Barnard, T. S.; Mason, M. R. Inorg. Chem. 2001, 40, 5001-5009.

139

110. Shi, Y. H.; Hall, C.; Ciszewski, J. T.; Cao, C. S.; Odom, A. L. Chem. Commun.

2003, 586-587.

111. Li, Y. H.; Turnas, A.; Ciszewski, J. T.; Odom, A. L. Inorg. Chem. 2002, 41, 6298-

6306.

112. Harris, S. A.; Ciszewski, J. T.; Odom, A. L. Inorg. Chem. 2001, 40, 1987-1988.

113. Mason, M. R. Chemtracts 2003, 16, 272-289.

114. Beer, P. D.; Drew, M. G. B.; Hesek, D.; Lacy, S. M. J. Organomet. Chem. 1996,

511, 207-215.

115. Schaaf, R. L.; Lenk, C. T. J. Org. Chem. 1964, 29, 3430-3433.

116. SMART, Software for the CCD Detector System; Siemens Analytical Instruments

Division: Madison, WI, 1995.

117. SAINT, Software for the CCD Detector System; Siemens Analytical Instruments

Division: Madison, WI, 1996.

118. Sheldrick, G. M. SADABS: Absorption Correction Program; University of

Göttingen: Göttingen, Germany 1996.

119. Sheldrick, G. M. Acta Crystallogr. Sect. A 2008, 64, 112-122.

120. Kamal, A.; Ali Qureshi, A. Tetrahedron 1962, 19, 513-520.

121. Zhang, Z. H.; Yin, L.; Wang, Y. M. Synthesis 2005, 1949-1954.

122. Shiri, M.; Ali Zolfigol, M.; Kruger, H. G.; Tanbakouchian, Z. Chem. Rev. 2010,

in press.

123. Laha, J. K.; Dhanalekshmi, S.; Taniguchi, M.; Ambroise, A.; Lindsey, J. S. Org.

Process Res. Dev. 2003, 7, 799-812.

140

124. Talbot, M. L.; Foster, T. T. Dicyclopentadienyl Iron Compounds. US Patent

3,673,232, June 27, 1972.

125. Cano, J.; Sudupe, M.; Royo, P.; Mosquera, M. E. G. Organometallics 2005, 24,

2424-2432.

126. Carpenetti, D. W.; Kloppenburg, L.; Kupec, J. T.; Petersen, J. L. Organometallics

1996, 15, 1572-1581.

127. Schrock, R. R. Acc. Chem. Res. 1990, 23, 158-165.

128. Manzer, L. E. Inorg. Synth. 1982, 21, 135-140.

129. Bradley, D. C.; Thomas, I. M. J. Chem. Soc. 1960, 3857.

130. Storozhenko, P. A.; Shcherbakova, G. I.; Tsirlin, A. M.; Florina, E. K.; Izmailova,

E. A.; Savitskii, A. A.; Kuznetsova, M. G.; Kuznetsova, T. M.; Stolyarova, I. V.;

Yurkov, G. Y.; Gubin, S. P. Inorg. Mater. 2006, 42, 1159-1167.

131. Chiu, H. T.; Chuang, S. H.; Tsai, C. E.; Lee, G. H.; Peng, S. M. Polyhedron 1998,

17, 2187-2190.

132. Korolev, A. V.; Rheingold, A. L.; Williams, D. S. Inorg. Chem. 1997, 36, 2647-

2655.

133. Dunn, S. C.; Batsanov, A. S.; Mountford, P. J. Chem. Soc. Chem. Commun. 1994,

2007-2008.

134. Blake, A. J.; Collier, P. E.; Dunn, S. C.; Li, W. S.; Mountford, P.; Shishkin, O. V.

J. Chem. Soc. Dalton Trans. 1997, 1549-1558.

135. Zhang, Y. T.; Mu, Y.; Lu, C. S.; Li, G. H.; Xu, J. S.; Zhang, Y. R.; Zhu, D. S.;

Feng, S. H. Organometallics 2004, 23, 540-546.

141

136. Hughes, A. K.; Marsh, S. M. B.; Howard, J. A. K.; Ford, P. S. J. Organomet.

Chem. 1997, 528, 195-198.

137. Wu, C. J.; Lee, S. H.; Yu, S. T.; Na, S. J.; Yun, H.; Lee, B. Y. Organometallics

2008, 27, 3907-3917.

138. Bordwell, F. G.; Bausch, M. J. J. Am. Chem. Soc. 1983, 105, 6188-6189.

139. Li, L. T.; Metz, M. V.; Li, H. B.; Chen, M. C.; Marks, T. J.; Liable-Sands, L.;

Rheingold, A. L. J. Am. Chem. Soc. 2002, 124, 12725-12741.

140. Balboni, D.; Camurati, I.; Prini, G.; Resconi, L.; Galli, S.; Mercandelli, P.; Sironi,

A. Inorg. Chem. 2001, 40, 6588.

141. McCoy, M.; Reisch, M. S.; Tullo, A. H.; Short, P. L.; Tremblay, J.-F.; Storck, W.

J. Facts & Figures of the Chemical Industry. Chemical & Engineering News, July

2, 2007, 29-69.

142. Kniel, L.; Winter, O.; Stork, K. Ethylene: Keystone to the Petrochemical

Industry; Marcel Dekker, Inc.: New York, 1980.

143. Ladwig, P. K. Handbook of Petroleum Refining Processes; Second ed.; McGraw-

Hill: New York, 1997.

144. Grantom, R. L.; Royer, D. J. Ullman's Encyclopedia of Industrial Chemistry;

Fifth ed.; VCH: New York, 1985; Vol. A10.

145. Safarik, D. J.; Eldridge, R. B. Ind. Eng. Chem. Res. 1998, 37, 2571-2581.

146. Eldridge, R. B. Ind. Eng. Chem. Res. 1993, 32, 2208-2212.

147. Jeanneret, J. J.; Mowry, J. R. Handbook of Petroleum Refining Processes; Second

ed.; McGraw-Hill: New York, 1997.

142

148. Sohn, S. W. Handbook of Petroleum Refining Processes; Second ed.; McGraw-

Hill: New York, 1997.

149. Dias, H. V. R.; Lovely, C. J. Chem. Rev. 2008, 108, 3223-3238.

150. Dewar, M. J. S. Bull. Soc. Chim. Fr. 1951, 71.

151. Chatt, J.; Duncanson, L. A. J. Chem. Soc. 1953, 2939-2947.

152. Zeise, W. C. Ann. Phys. 1827, 9, 932.

153. Wang, K.; Stiefel, E. I. Science 2001, 291, 106-109.

154. Padin, J.; Yang, R. T. Chem. Eng. Sci. 2000, 55, 2607-2616.

155. Eberz, W. F.; Welge, H. J.; Yost, D. M.; Lucas, H. J. J. Am. Chem. Soc. 1937, 59,

45.

156. Winstein, S.; Lucas, H. J. J. Am. Chem. Soc. 1938, 60, 836.

157. Goering, R. M.; Bowman, C. N.; Koval, C. A.; Noble, R. D.; Ashley, M. E. J.

Membr. Sci. 2000, 172, 49-57.

158. Quin, H. W.; Tsai, J. H. Adv. Inorg. Chem. Radiochem. 1969, 12, 217-373.

159. Camus, A.; Marsich, N.; Nardin, G.; Randaccio, L. Inorg. Chim. Acta 1977, 23,

131-144.

160. Yanagihara, N.; Sampedro, J. A.; Casillas, R.; Fernando, Q.; Ogura, T. Inorg.

Chem. 1982, 21, 475-479.

161. Hakansson, M.; Jagner, S.; Walther, D. Organometallics 1991, 10, 1317-1319.

162. Suzuki, T.; Noble, R. D.; Koval, C. A. Inorg. Chem. 1997, 36, 136-140.

163. Pasquali, M.; Floriani, C.; Gaetani-Manfredotti, A.; Chiesi-Villa, A. Inorg. Chem.

1979, 18, 3535-3542.

143

164. Masuda, H.; Yamamoto, N.; Taga, T.; Machida, K.; Kitagawa, S.; Munakata, M.

J. Organomet. Chem. 1987, 322, 121-129.

165. Hu, C.; Veldman, N.; Spek, A. L.; Averill, B. A. Synthesis, Crystallographic and

NMR Studies of Cu(I)-Amine Complexes with Ethylene, Carbonyl, and

Acetylene., University of Amsterdam, Amsterdam, Netherlands, 1998.

166. Davis, J. C.; Valus, R. J. Removal of Olefins from Mixtures Thereof.

EP19950305762 19950817, March 6, 1996.

167. Helmstadter, M. D. M.S. Thesis, The University of Toledo, 2006.

168. Kubas, G. J. Inorg. Synth. 1979, 29, 90-92.

169. Oki, M. Applications of Dynamic NMR Spectroscopy to Organic Chemistry;

VCH: New York, 1985.

144

Appendix 1

Metallophosphinates and Phosphonates of Aluminum and Gallium

A.1 Introduction

Zeolitic materials, a family of porous, crystalline aluminosilicates, have been used in a variety of industrial applications throughout the years.170 Industrially, zeolites are of interest due to their remarkable thermal stability and the micro- and mesoporous frameworks they possess.171 These attributes make them particularly attractive to the petroleum industry for use in catalytic cracking of crude oil. One major drawback to zeolites is their relatively small pore size (up to ~10 Å). Cracking of large organic molecules contained in the heavy fractions of crude oil is impossible with this limited size. Various research efforts are in progress to produce three-dimensional arrays that mimic zeolites and also have pore sizes larger than 10 Å. Two methodologies are typically used for the creation of these materials: 1) synthesis with structure-directing agents or 2) assembly of small molecule linkages.

The use of surfactants as structure-directing agents has gained industrial interest specifically in the development of MCM-41 materials.172,173 Depending on the structure- directing agent used, large pore materials like MCM-41 can be synthesized with pore sizes ranging from 15 Å to 200 Å. The ability to tune the pore size of these materials makes them very attractive for industrial applications. The major drawback of these

145 types of materials, however, is that at high temperatures these materials undergo structural collapse. Consequently their industrial use has been limited, and a more thermally stable porous material is desirable.

Aluminophosphates (AlPO4) and gallophosphates (GaPO4) have been studied for several uses such as molecular sieve materials,170 catalysts, and catalyst supports.174

Development of group 13 secondary building units (SBUs) originated from the development of a large three-dimensional structure, cloverite, which is assembled through double-four ring (D4R) gallophosphate linkages.175 Secondary building units are a set of structural units commonly found in zeolitic materials (Figure A.1). In fact, several other SBUs composed of single-ring (nR, n = 4, 5, 6, 8) and double ring structures (DnR, n = 4, 5, 6, 8) have been reported. The structure of cloverite, possesses a pore size of 13 Å, and the inner cavity of the supercage (corner to corner) has a diameter of 29 Å. Substrates can enter through the small pore and catalytic transformation can occur via reaction at Bronsted acidic sites inside the larger cage structure. This feature makes these types of materials attractive for use in chemical transformations.

4R D4R D6R D8R = P = M

Figure A.1. Some typical secondary building units (SBU). Bridging 2-oxo

atoms along each edge are omitted for clarity.

146

Small molecule synthesis was also aimed at creating a family of silicon based

176-182 compounds called silsesquioxanes (RSiO1.5)n. In fact, octameric silsesquioxanes

(R8Si8O12) were modeled after SBUs, and are composed of a double-four ring structure.

These compounds have been examined for several uses, and their synthesis in the presence of a structure directing agent such as tetrabutylammonium fluoride has been investigated.177-179 Bassindale et al. have demonstrated that D4R silsesquioxanes are

n 179 formed preferentially in the presence of Bu4NF.

Recent research efforts focused on the development of three-dimensional frameworks assembled from SBUs. Secondary building units based on aluminophosphate and gallophosphate frameworks have been an area of interest for several research groups such as Mason,183-186 Roesky,187 Bonhomme,188-191 Murugavel,192 and others.193,194 Progress in this area has resulted in a series of alumino- and gallo- phosphinates, phosphonates, and phosphates by reaction of metal alkyls with phosphinic, phosphonic, or phosphoric acids, respectively. These compounds have been studied for

195 catalytic applications directly, specifically in the polymerization of epoxides.

Our initial focus in these studies was to synthesize alumino- and gallo- phosphinates and phosphonates that feature aryl groups on the metal centers and alkyl or aryl groups on the phosphorus atoms. Currently, there are no SBUs reported in the literature for arylalumino- or arylgallo-phosphinates or phosphonates. Clearfield et al. have reported some layered materials synthesized from arylaluminum precursors, although discrete building units were not reported.196,197 Aluminum and gallium aryl precursors are easily synthesized in high yields via reaction of metal chlorides and aryl

Grignard reagents.198 The next step in this method was to synthesize SBUs with organic

147 linking groups at the phosphorus atoms such as benzonitrile or pyridyl groups.

Furthermore, derivatization of the aryl groups on aluminum or gallium with organic linker groups could result in the formation of three-dimensional porous frameworks.

These types of SBUs have been previously prepared with aluminum alkyl precursors, and aryl SBUs may lead to different chemical or industrial applications.199

In this appendix, the syntheses and partial characterization of alumino- and gallophosphinate and phosphonhate compounds are discussed. Also reported are the syntheses and partial characterization of products from reactions of triphenylaluminum and triphenylgallium with various phosphonic acids. While these reactions produced solid products that precipitated out of the reaction solutions, their insoluble nature and amorphous composition hindered NMR and crystallographic characterization. Infrared and thermogravimetric data of some of these products are presented.

A.2 Experimental

General Procedures

All air- and moisture-sensitive reactions were performed in an inert atmosphere of purified nitrogen using standard inert atmosphere techniques and an Innovative

Technologies dry box. Toluene was distilled from sodium, hexanes were distilled from calcium hydride, and diethyl ether and tetrahydrofuran were distilled from sodium benzophenone ketyl prior to use. Diphenylphosphinic acid, diphenylphosphate, methylphosphonic acid, and phenylphosphonic acid were purchased from Aldrich and used without further purification. Ph3Al OEt2 and Ph3Ga OEt2 were synthesized

198 according to literature procedures. Chloroform-d and benzene-d6 were dried by

148 storage over activated molecular sieves. Solution NMR spectra were recorded on Varian

Inova 600 (1H, 13C), Varian Unity 400 and Varian Gemini 200 (31P, 81 MHz) spectrometers using a deuterated solvent as an internal lock. Chemical shifts are reported

1 13 31 relative to TMS ( H, C) and 85% H3PO4 ( P). Infrared spectra were recorded on a

Perkin Elmer GX FT-IR infrared spectrometer. Thermal gravimetric-differential thermal analysis data were recorded on a TA Instruments SDT 2960 Simultaneous DTA-TGA instrument.

Preparation of Ph3Al OEt2

198 Using a method analogous to that reported by Mole et al., AlCl3 (10.0 g, 75.0 mmol) was dissolved in 50 mL diethyl ether. A solution of phenylmagnesium bromide

(75 mL, 3.0 M in diethyl ether, 0.23 mol) was added and the resulting mixture was stirred at room temperature for 12 h. This light grey slurry was concentrated to half of the original volume, and toluene was added (70 mL). The mixture was heated and filtered hot to remove magnesium halide, leaving a yellow filtrate. The solution was concentrated in vacuo and placed in a freezer ( 30 C) overnight. A white solid was isolated by filtration and dried in vacuo. Spectral resonances of 1H NMR matched

198 1 literature values. Yield: 19.8 g, 60.0 mmol, 80%. H NMR (benzene-d6, 600 MHz):

7.80 (m, 6H), 7.38 (m, 6H) 7.33 (m, 3H), 3.42 (q, 4H, CH2CH3), 0.51 (t, 6H, CH2CH3).

Preparation of Ph3Ga OEt2

Triphenyl gallium etherate was prepared in an analogous method as described for

1 200 Ph3Al OEt2. Spectral resonances of H NMR matched literature values. Yield: 12.9

149

1 g, 0.035 mol, 46%. H NMR (CDCl3, 600 MHz): 7.80 (m, 6H), 7.38 (m, 9H), 3.74 (q,

4H, CH2CH3), 1.08 (t, 6H, CH2CH3).

Synthesis of [Ph2AlO2PPh2] (A)

Triphenylaluminum etherate (2.01 g, 6.02 mmol) was dissolved in 10 mL of THF.

A solution of diphenylphosphinic acid (1.31 g, 6.02 mmol) in 10 mL of THF was added via cannula. Upon addition, heat was released, and the resulting yellow reaction solution was stirred at room temperature for 12 h. The reaction solution was concentrated in vacuo, and clear, colorless crystals formed at 30 C. Yield: 2.45 g, 3.01 mmol, 51%. 1H

NMR (benzene-d6, 600 MHz): 7.95 (m, 8H), 7.60 (dd, 8H), 7.29 (m, 8H), 6.87 (t, 8H),

13 1 6.75 (m, 8H). C{ H} NMR (benzene-d6, 150 MHz): 138.0 (s, ortho Al-Ph), 132.5 (d,

4J(P,C) = 2.85 Hz, para), 131.4 (d, 2J(P,C) = 11.4 Hz, ortho), 130.5 (d, 1J(P,C) = 149.3

Hz, ipso), 128.6 (d, 3J(P,C) = 14.3 Hz, meta), 128.0 (s, para Al-Ph), 127.4 (s, meta Al-

31 1 Ph). P{ H} NMR (benzene-d6, 81 MHz): 27.2.

Synthesis of [Ph2GaO2PPh2]2 (B)

Triphenylgallium etherate (2.01 g, 5.30 mmol) was dissolved in 10 mL of THF.

A solution of diphenylphosphinic acid (1.16 g, 5.30 mmol) in 10 mL of THF was added via cannula. The resulting colorless reaction solution was refluxed for 12 h. Volatiles were removed in vacuo, leaving a white residue that was washed with toluene (1 10 mL). Attempts to crystallize this product through various methods were unsuccessful.

Poor solubility hindered characterization by 13C NMR spectroscopy. Yield: 1.87 g, 2.12

1 mmol, 40%. H NMR (benzene-d6, 600 MHz): 8.11 (m, broad, 4H), 8.05 (m, broad,

150

4H), 7.95 (d, 4H), 7.88 (m, broad, 8H), 7.32 (t, 4H) 7.22 (t, 4H), 7.05 (t, 4H), 7.01 (m,

31 1 4H). P{ H} NMR (benzene-d6, 81 MHz): 21.2 (broad).

Reaction of Ph3Al OEt2 and (PhO)2PO(OH) (C)

Triphenylaluminum etherate (1.00 g, 3.01 mmol) was dissolved in 10 mL of THF.

A solution of diphenyl phosphate (0.753 g, 3.01 mmol) in 10 mL of THF was added via cannula. Upon addition, heat was released and the resulting colorless reaction solution was stirred at room temperature for 12 h. Volatiles were removed in vacuo leaving a white residue. Attempts to obtain crystalline material from concentrated solutions of THF

1 or toluene were unsuccessful. Yield: 1.19 g, 1.35 mmol, 45%. H NMR (CDCl3, 600

MHz): 7.79 (m, 4H), 7.47 (d, 4H), 7.34 (m, 4H), 7.28 (m, 4H), 7.18 (m, 8H), 7.15 (t,

31 1 4H), 7.11 (m, 8H), 6.86 (m, 4H). P{ H} NMR (CDCl3, 81 MHz): 22.1 (broad),

24.2.

Synthesis of [Ph2GaO2P(OPh)2]2 (D)

Triphenylgallium etherate (1.00 g, 2.67 mmol) was dissolved in 15 mL of THF.

A solution of diphenyl phosphate (0.667 g, 2.67 mmol) in 15 mL of THF was added via cannula. The colorless reaction solution was refluxed for 12 h. Volatiles were removed in vacuo, leaving a white residue. Clear, colorless crystals were obtained from a concentrated toluene solution at 30 C. Poor solubility of D limited characterization by

13 1 C NMR spectroscopy. Yield: 1.16 g, 1.23 mmol, 46%. H NMR (benzene-d6, 600

MHz): 7.32 (m, 8H), 7.28 (m, 4H), 7.14 (d, 8H), 7.11 (t, 8H), 7.04 (m, 4H), 6.91 (m,

151

31 1 8H). P{ H} NMR (benzene-d6, 81 MHz): 13.38 (minor), 14.54 (minor) 15.9

(major).

Reaction of Ph3Al OEt2 and PhPO(OH)2

Triphenylaluminum etherate (1.66 g, 5.00 mmol) was dissolved in 10 mL of THF.

A solution of phenylphosphonic acid (0.79 g, 5.0 mmol) in 5 mL of THF was added via cannula. Upon addition, heat was released, and the reaction mixture was stirred for 1 h at room temperature. A white precipitate formed, and the mixture was concentrated in vacuo and placed in a freezer overnight at 30 C. The white solid was isolated by filtration and dried in vacuo. The product was insoluble, and NMR data were not obtained. IR (KBr, cm-1): 3060 (s), 2986 (s), 2904 (s), 2742 (w), 2344 (w), 1964 (w),

1894 (w), 1820 (w), 1775 (w), 1679 (w), 1597 (m), 1489 (m), 1439 (s), 1421 (m), 1160

(s, br), 922 (m), 879 (m).

Reaction of Ph3Al OEt2 and MePO(OH)2 (Method 1)

Toluene (10 mL) was added to triphenylaluminum etherate (1.72 g, 5.18 mmol) creating a white slurry. A slurry of methylphosphonic acid (0.510 g, 5.18 mmol) in toluene (10 mL) was added in portions via cannula. The cloudy white mixture was refluxed for 12 h. After cooling to room temperature, a clear, colorless solid formed.

This solid was isolated by filtration and dried in vacuo. The product was insoluble and

NMR data were not obtained.

152

Reaction of Ph3Al OEt2 and MePO(OH)2 (Method 2)

Triphenylaluminum etherate (1.00 g, 3.01 mmol) was dissolved in 20 mL of THF.

A solution of methylphosphonic acid (0.146 g, 1.51 mmol) in 10 mL of THF was added via cannula. The colorless reaction mixture was stirred at room temperature for 12 h.

1 Volatiles were removed in vacuo, leaving a white residue. H NMR (CDCl3, 200 MHz):

2 31 1 7.79 (m, 4H), 7.63 (m, 4H), 7.32 (m, 8H), 1.61 (d, JPH = 19.4 Hz, 3H). P { H}

(CDCl3, 81 MHz): 12.18.

Reaction of Ph3Ga OEt2 and MePO(OH)2

Triphenylgallium etherate (1.40 g, 4.67 mmol) was stirred in 10 mL of THF. A solution of methylphosphonic acid (0.45 g, 4.7 mmol) in 10 mL of THF was added via cannula. The clear, pale yellow reaction solution was stirred at room temperature for 12 h. Volatiles were removed in vacuo, and dissolved in 10 mL of hot toluene. After addition of 10 mL of hexanes, a white precipitate formed. The solid was isolated by filtration and dried in vacuo. The product was insoluble and NMR data could not be obtained. Infrared spectral data did not provide structural information.

A.3 X-Ray Crystallography

Crystals of A were grown from a concentrated toluene solution stored at 30 °C.

X-ray diffraction data were collected on a Siemens three-circle platform diffractometer equipped with a 4K CCD detector. The frame data were collected with the SMART

5.625116 software using Mo K radiation ( = 0.71073 Å). Cell constants were determined with SAINT 6.22117 from the complete data set. A complete hemisphere of

153 data was collected using (0.3°) scans with a run time of 30 s/frame at different angles. The frames were integrated using the SAINT 6.22 software and the data were corrected for absorption and decay using the SADABS118 program. The structures were solved by direct methods and refined by least-squares methods on F2, using the

SHELXTL program suite.119 The structure for A was initially solved with direct methods in the P1 space group. The initial structure shows four molecules in the asymmetric unit. For A there are disordered phenyl groups on several of the aluminum and phosphorus atoms in these molecules, which cannot be modeled successfully. Attempts to model the structure in different space groups did not prove to be successful.

A.4 Results and Discussion

Triphenylaluminum etherate and triphenylgallium etherate can be synthesized in good yields by reacting phenylmagnesium bromide with aluminum chloride and gallium chloride, respectively, according to Mole‟s method (eq. 1).198 Use of trialkyl aluminum and gallium reagents in the synthesis of 4R, D4R, and D6R compounds with phosphonic and phosphinic acids has been achieved by the Mason group.183-185,199,201,202 Therefore, we reasoned that reaction of triphenyl aluminum and gallium reagents with phosphinic and phosphonic acids should produce 4R and D4R compounds in a straightforward manner. Triphenylaluminum and triphenylgallium were chosen as initial reactants since the use of aryl groups with appropriate substituents in the para position could act as rigid linkers to other structural units. This would allow for the formation of three-dimensional frameworks similar to metal-organic framework (MOF) materials.203-206

154

Et2O MCl + 3 PhMgBr Ph M·OEt 3 toluene 3 2 (1) - 3 MgBrCl M = Al, Ga

Equimolar reaction of triphenylaluminum and triphenylgallium with diphenylphosphinic acid in THF at room temperature and at reflux, respectively, produced 4R alumino- (A) and gallophosphinate (B) compounds in moderate yields (eq.

2). Characterization of these compounds was relatively straightforward, and they exhibited 1H and 31P NMR spectra similar to previously reported 4R compounds.183

Complete characterization was hindered, however, by significant broadening and overlaps in the 1H NMR spectrum for compound B.

Ph Ph P O O THF Ph Ph 2 Ph3M·OEt2 + 2 Ph2PO(OH) M M (2) - 2 C6H6 Ph O O Ph P Ph Ph M = Al (A), Ga (B)

Upon reaction of triphenylaluminum with diphenylphosphinic acid, heat was released, and a yellow reaction solution resulted. After room temperature reaction for 12 h, concentration of the reaction solution and storage at 30 C produced colorless crystals of A. There was a single 31P resonance for compound A at 27.2 ppm. Free diphenylphosphinic acid was not soluble in benzene-d6 (Figure A.2). Proton NMR data showed the absence of coordinated ether, and aromatic proton resonances for starting materials were replaced by new resonances. Multiplet resonances were observed at 7.95,

155

7.29, and 6.75 ppm. A doublet of doublets resonance was seen at 7.60 ppm, and a triplet resonance was observed at 6.87 ppm. The integration and relative sharpness of these resonances suggested a symmetrical structure in solution. Further evidence of a symmetrical 4R structure was observed in the 13C NMR spectrum. The 1H, 13C and 31P

NMR spectra were all consistent with a symmetrical structure. X-ray quality crystals of

A formed in concentrated solutions of toluene. X-ray structural analysis confirmed a dimeric structure with a 4R Al2P2O4 ring arrangement of the type [Ph2AlO2PPh2]2.

Repeated attempts to fully model this structure were hindered by disorder of several phenyl groups.

31 Figure A.2. P NMR spectrum of [Ph2Al2O2PPh2]2.

The reaction of triphenylgallium etherate with diphenylphosphinic acid in refluxing THF produced compound B in moderate yield. After refluxing the clear and colorless reaction solution for 12 hours, volatiles were removed in vacuo, which resulted in the formation of a colorless solid. Repeated attempts at recrystallizing B from concentrated solutions of THF, toluene, and mixtures with hexanes were unsuccessful.

156

Proton NMR resonances of B suggested product formation, although complete characterization of the compound was hindered by broadening in the aromatic region.

Furthermore, the presence of THF resonances shifted from free THF suggested some coordinative bonding to the gallium atoms. Characterization by 31P NMR was also ambiguous, and a single broad resonance for B was observed at 21.2 ppm. Free diphenylphosphinic acid is not soluble in benzene-d6.

Equimolar reaction of triphenylaluminum and triphenylgallium with diphenylphosphate in THF at room temperature and at reflux, respectively, produced 4R alumino- (C) and gallophosphate (D) compounds in moderate yields (eq. 3).

Characterization of these compounds was not straightforward, although they exhibited 1H and 31P NMR spectra similar to previously reported 4R compounds.184,185 Complete characterization was hindered by significant broadening and overlaps in the 1H NMR spectra for compound C and D.

OPh OPh P O O THF R R 2 Ph3M·OEt2 + 2 (PhO)2PO(OH) M M (3) - 2 C6H6 R O O R P OPh OPh

M = Al (C), Ga (D)

Compound C was formed by reaction of triphenylaluminum etherate and diphenylphosphate in THF at room temperature for 12 hours. Initially, heat was released from the reaction solution, which resulted in a clear, colorless reaction solution.

Evaporation of the solvent resulted in a colorless solid residue. Attempts to recrystallize

157 from concentrated solutions of THF, toluene, or mixtures of these solvents with hexanes were unsuccessful. Aryl resonances were broad, and overlapping aromatic proton resonances, as well as broad resonances of THF at 3.83 ppm and 1.77 ppm, suggested coordinative bonding to the aluminum atoms. However, 31P NMR revealed two resonances, a minor broad resonance at 22.1 ppm and a major sharp singlet resonance at

24.2 ppm, both of which were significantly shifted from starting diphenylphosphate

( 9.5 ppm). The shifts in the 31P NMR data suggested either partial product formation or an asymmetric structure.

Compound D was formed by reaction of triphenylgallium etherate and diphenylphosphate in refluxing THF. Removal of the solvent from the clear, colorless reaction solution and redissolvation in a minimal amount of toluene produced D in moderate yield as a colorless crystalline material that was not suitable for X-ray diffraction. Repeated attempts to produce X-ray quality crystals from various solvent combinations were unsuccessful. Structural characterization by 1H NMR also proved difficult, as broadening and resonance overlap were observed. Resonances for THF were observed at 3.56 ppm and 1.40 ppm, suggesting coordinative bonding to the gallium atoms. A major singlet resonance was observed by 31P NMR at 15.1 ppm, significantly shifted from that of free diphenylphosphate ( ppm). Two minor singlet resonances were also observed in the 31P spectrum at 13.4 ppm and 14.5 ppm (Figure A.3). The presence of multiple resonances in the 31P spectrum suggested two possible scenarios: 1) more than one product crystallized out of solution, or 2) the product possessed an asymmetric structure.

158

Figure A.3. 31P NMR spectrum of D.

Based on previous results by the Mason group, synthesis of D4R structures via reaction of triphenyl group 13 reagents and phosphonic acids was believed to be straightforward.183,185,199 Previous reports using trialkyl aluminum and gallium reagents had produced several D4R structures upon reaction with phosphonic acids. However, reaction of triphenylaluminum and triphenylgallium with phosphonic acids was not straightforward, and produced insoluble solid materials that were considerably more difficult to characterize with traditional NMR and crystallographic methods. In these instances, infrared spectroscopy, powder X-ray diffraction, and thermogravimetric analysis-differential thermal analysis were attempted, although no distinct structural determination could be accomplished. Synthesis with the assistance of a structure directing agent, tetrabutylammonium fluoride, was also employed. This reagent has proven useful in the formation of silsesquioxane D4R units.177-179 In this research,

n however, the use of Bu4NF was unsuccessful in forming D4R metallophosphonate units.

Reaction of triphenylaluminum etherate with phenylphosphonic acid in THF at room temperature immediately resulted in an insoluble white solid. After stirring at room

159 temperature for 12 h, the white solid was isolated by filtration and dried in vacuo.

Concentration of the clear, colorless reaction solution and storage at 30 C for three days resulted in the formation of colorless crystals that were not suitable for X-ray characterization, and did not dissolve in traditional NMR solvents. Characterization by

IR spectroscopy (KBr pellet) and TG-DTA was attempted, although distinct structural information could not be obtained. TG-DTA analysis revealed weight losses of 22.78% from 47.84 C to 287.4 C, 11.22% from 519.2 C to 710.0 C, and 24.32% from 1085

C to 1152 C. Complete thermal decomposition was observed at 1189 C. The solid material was amorphous, which precluded characterization by Powder XRD.

Equimolar reaction of triphenylaluminum etherate and methylphosphonic acid in refluxing toluene initially produced a clear, colorless solution. After refluxing for 12 h and cooling to room temperature, a colorless solid formed, which was isolated by filration and dried in vacuo. This solid was insoluble in traditional NMR solvents, and characterization of this solid via IR spectroscopy (KBr pellet) provided no structural information. Further investigation into reactivity was performed by reaction of triphenylaluminum etherate and one-half equivalent of methylphosphonic acid. A clear, colorless reaction solution resulted after stirring at room temperature for 12 hours.

Removal of the solvent in vacuo left a colorless solid residue, which was dissolved in

1 CDCl3 for NMR characterization. Multiplet resonances were observed in the H NMR spectrum at 7.79 ppm , 7.63 ppm, and 7.32 ppm. Resonances for THF were also observed at 3.98 ppm and 1.91 ppm which are shifted from free THF, suggesting coordinative bonding. A small doublet was observed at 1.61 ppm, shifted from that of

2 free methylphosphonic acid, with a JPH coupling constant of 19.4 Hz, which was in

160 agreement with typical phosphorus-proton coupling constants. A singlet resonance in the

31P NMR spectrum was observed at 12.2 ppm. Repeated attempts to recrystallize this solid for further structural characterization were unsuccessful.

Reaction of triphenylgallium etherate and methylphosphonic acid in THF resulted in a pale yellow reaction solution, which was stirred at room temperature for 12 h. After workup, a white precipitate was isolated by filtration and dried in vacuo. Infrared spectroscopic data (KBr pellet) did not provide any useful structural data.

A.5 Conclusions

This appendix reports the initial studies of reactions of triphenylaluminum and triphenylgallium with phosphonic and phosphinic acids. While synthesis and characterization of 4R structures based on aryl group 13 starting materials was successful, reaction of triphenylaluminum and triphenylgallium with phosphonic acids results in insoluble materials with no indication that D4R units have been created.

Further reactivity of these reagents in the formation of D4R structural units should be explored.

161

A.6 References

170. Dyer, A. An Introduction to Zeolite Molecular Sieves; John Wiley & Sons Ltd.:

New York, 1988.

171. Breck, D. W. Zeolite Molecular Sieves: Structure, Chemistry, and Use; Wiley-

Interscience: New York, 1974.

172. Rubin, M. K.; Chu, P. Composition of Synthetic Porous Crystalline Material, Its

Synthesis and Use. U.S. Patent 4954325, September 4, 1990.

173. Kresge, C. T.; Leonowicz, M. E.; Roth, W. J.; Vartuli, J. C.; Beck, J. S. Nature

1992, 359, 710-712.

174. Weitkamp, J.; Puppe, L. Catalysis and Zeolites: Fundamentals and Applications;

Springer: Berlin, 1999.

175. Estermann, M.; McCusker, L. B.; Baerlocher, C.; Merrouche, A.; Kessler, H.

Nature 1991, 352, 320-323.

176. Harrison, P. G. J. Organomet. Chem. 1997, 542, 141-183.

177. Bassindale, A. R.; Pourny, M.; Taylor, P. G.; Hursthouse, M. B.; Light, M. E.

Angew. Chem. Int. Ed. Engl. 2003, 42, 3488-3490.

178. Bassindale, A. R.; Parker, D. J.; Pourny, M.; Taylor, P. G.; Horton, P. N.;

Hursthouse, M. B. Organometallics 2004, 23, 4400-4405.

179. Bassindale, A. R.; Chen, H. P.; Liu, Z. H.; MacKinnon, L. A.; Parker, D. J.;

Taylor, P. G.; Yang, Y. X.; Light, M. E.; Horton, P. N.; Hursthouse, M. B. J.

Organomet. Chem. 2004, 689, 3287-3300.

180. Bassindale, A. R.; Gentle, T. E. J. Mater. Chem. 1993, 3, 1319-1325.

162

181. Bonhomme, C.; Toledano, P.; Maquet, J.; Livage, J.; Bonhomme-Coury, L. J.

Chem. Soc. Dalton Trans. 1997, 1617-1626.

182. Feher, F. J.; Wyndham, K. D.; Soulivong, D.; Nguyen, F. J. Chem. Soc. Dalton

Trans. 1999, 1491-1497.

183. Mason, M. R.; Mashuta, M. S.; Richardson, J. F. Angew. Chem. Int. Ed. 1997, 36,

239-241.

184. Mason, M. R.; Matthews, R. M.; Mashuta, M. S.; Richardson, J. F. Inorg. Chem.

1996, 35, 5756.

185. Mason, M. R.; Perkins, A. M.; Matthews, R. M.; Fisher, J. D.; Mashuta, M. S.;

Vij, A. Inorg. Chem. 1998, 37, 3734-3746.

186. Mason, M. R.; Perkins, A. M.; Ponomarova, V. V.; Vij, A. Organometallics 2001,

20, 4833-4839.

187. Yang, Y.; Walawalkar, M. G.; Pinkas, J.; Roesky, H. W.; Schmidt, H. G. Angew.

Chem. Int. Ed. 1998, 37, 96-98.

188. Azais, T.; Bonhomme, C.; Bonhomme-Coury, L.; Kickelbick, G. Dalton Trans.

2003, 3158-3159.

189. Azais, T.; Bonhomme, C.; Bonhomme-Coury, L.; Vaissermann, J.; Millot, Y.;

Man, P. P.; Bertani, P.; Hirschinger, J.; Livage, J. J. Chem. Soc. Dalton Trans.

2002, 609-618.

190. Azais, T.; Bonhomme-Coury, L.; Vaissermann, J.; Bertani, P.; Hirschinger, J.;

Maquet, J.; Bonhomme, C. Inorg. Chem. 2002, 41, 981-988.

191. Azais, T.; Bonhomme-Coury, L.; Vaissermann, J.; Maquet, J.; Bonhomme, C.

Eur. J. Inorg. Chem. 2002, 2838-2843.

163

192. Murugavel, R.; Kuppuswamy, S. Angew. Chem. Int. Ed. 2006, 45, 7022-7026.

193. Mitra, A.; Parkin, S.; Atwood, D. A. Inorg. Chem. 2006, 45, 3970-3975.

194. Wragg, D. S.; Slawin, A. M. Z.; Morris, R. E. J. Mater. Chem. 2001, 11, 1850-

1857.

195. Mason, M. R.; Perkins, A. M. J. Organomet. Chem. 2000, 599, 200-207.

196. Cabeza, A.; Aranda, M. A. G.; Bruque, S.; Poojary, D. M.; Clearfield, A.; Sanz, J.

Inorg. Chem. 1998, 37, 4168-4178.

197. Gomez-Alcantara, M. D.; Cabeza, A.; Moreno-Real, L.; Aranda, M. A. G.;

Clearfield, A. Microporous Mesoporous Mater. 2006, 88, 293-303.

198. Mole, T. Aust. J. Chem. 1963, 16, 794-800.

199. Matthews, R. M. Ph.D. Dissertation, The University of Louisville, 2000.

200. Miller, S. B.; Jelus, B. L.; Smith, J. H.; Munson, B.; Brill, T. B. J. Organomet.

Chem. 1979, 170, 9-19.

201. Mason, M. R. J. Cluster Sci. 1998, 9, 1-23.

202. Mason, M. R.; Matthews, R. M.; Perkins, A. M.; Ponomarova, V. V. In Group 13

Chemistry: From Fundamentals to Applications; Shapiro, P. J., Atwood, D. A.,

Eds. 2002; Vol. 822, p 181-194.

203. Yaghi, O. M.; Li, H. L.; Davis, C.; Richardson, D.; Groy, T. L. Acc. Chem. Res.

1998, 31, 474-484.

204. Eddaoudi, M.; Moler, D. B.; Li, H. L.; Chen, B. L.; Reineke, T. M.; O'Keeffe, M.;

Yaghi, O. M. Acc. Chem. Res. 2001, 34, 319-330.

205. Rowsell, J. L. C.; Yaghi, O. M. Angew. Chem. Int. Ed. 2005, 44, 4670-4679.

164

206. Chen, B. L.; Ockwig, N. W.; Millward, A. R.; Contreras, D. S.; Yaghi, O. M.

Angew. Chem. Int. Ed. 2005, 44, 4745-4749.

165

Appendix 2

CIF Files for Compounds

CIF File for H3FDI·THF

_audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common _chemical_melting_point _chemical_formula_moiety 'C37 H36 N2 O' _chemical_formula_sum 'C37 H36 N2 O' _chemical_formula_weight 524.68 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source 'C' 'C' 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'H' 'H' 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'N' 'N' 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'O' 'O' 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M P2(1)/n loop_

166

_symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, y+1/2, -z+1/2' '-x, -y, -z' 'x-1/2, -y-1/2, z-1/2'

_cell_length_a 10.5616(10) _cell_length_b 9.5966(9) _cell_length_c 28.719(3) _cell_angle_alpha 90.00 _cell_angle_beta 90.592(2) _cell_angle_gamma 90.00 _cell_volume 2910.7(5) _cell_formula_units_Z 4 _cell_measurement_temperature 140(2) _cell_measurement_reflns_used 6336 _cell_measurement_theta_min 1.80 _cell_measurement_theta_max 25.24

_exptl_crystal_description 'cubic' _exptl_crystal_colour 'colorless' _exptl_crystal_size_max .40 _exptl_crystal_size_mid .40 _exptl_crystal_size_min .12 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.197 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1120 _exptl_absorpt_coefficient_mu 0.071 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.830 _exptl_absorpt_correction_T_max 1.000 _exptl_absorpt_process_details ?

_exptl_special_details ; ? ;

167

_diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 16039 _diffrn_reflns_av_R_equivalents 0.0213 _diffrn_reflns_av_sigmaI/netI 0.0262 _diffrn_reflns_limit_h_min -13 _diffrn_reflns_limit_h_max 13 _diffrn_reflns_limit_k_min -11 _diffrn_reflns_limit_k_max 9 _diffrn_reflns_limit_l_min -33 _diffrn_reflns_limit_l_max 33 _diffrn_reflns_theta_min 2.05 _diffrn_reflns_theta_max 25.99 _reflns_number_total 5441 _reflns_number_gt 4828 _reflns_threshold_expression >2sigma(I)

_computing_data_collection 'Smart 5.630' _computing_cell_refinement 'Saintplus 5.45' _computing_data_reduction 'Saintplus 5.45' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ? _computing_publication_material ?

_refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ;

_refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0547P)^2^+1.8117P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap

168

_atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment mixed _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 5441 _refine_ls_number_parameters 481 _refine_ls_number_restraints 12 _refine_ls_R_factor_all 0.0644 _refine_ls_R_factor_gt 0.0571 _refine_ls_wR_factor_ref 0.1435 _refine_ls_wR_factor_gt 0.1388 _refine_ls_goodness_of_fit_ref 1.085 _refine_ls_restrained_S_all 1.100 _refine_ls_shift/su_max 0.007 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group N1 N 0.50136(14) 0.06119(18) 0.22035(6) 0.0343(4) Uani 1 1 d . . . N2 N 0.30035(14) 0.03438(18) 0.13346(6) 0.0341(4) Uani 1 1 d . . . C1 C 0.52168(16) 0.1307(2) 0.13638(7) 0.0309(4) Uani 1 1 d . . . C2 C 0.57714(16) -0.0085(2) 0.11960(7) 0.0316(4) Uani 1 1 d . . . C3 C 0.56425(16) -0.0408(2) 0.06707(7) 0.0323(4) Uani 1 1 d . . . C10 C 0.54991(15) 0.15180(19) 0.18733(7) 0.0311(4) Uani 1 1 d . . . C11 C 0.62051(16) 0.2526(2) 0.20935(7) 0.0340(4) Uani 1 1 d . . . C12 C 0.61505(16) 0.2238(2) 0.25838(7) 0.0341(4) Uani 1 1 d . . . C13 C 0.66690(19) 0.2876(2) 0.29842(8) 0.0420(5) Uani 1 1 d . . . C14 C 0.6425(2) 0.2312(2) 0.34138(8) 0.0454(5) Uani 1 1 d . . . C15 C 0.56682(19) 0.1128(2) 0.34595(8) 0.0428(5) Uani 1 1 d . . . C16 C 0.51419(18) 0.0470(2) 0.30760(7) 0.0381(5) Uani 1 1 d . . . C17 C 0.54009(16) 0.1039(2) 0.26400(7) 0.0322(4) Uani 1 1 d . . . C18 C 0.6940(2) 0.3682(3) 0.18737(9) 0.0495(6) Uani 1 1 d . . . C20 C 0.38139(16) 0.1453(2) 0.12584(6) 0.0311(4) Uani 1 1 d . . . C21 C 0.31396(18) 0.2593(2) 0.11143(7) 0.0375(4) Uani 1 1 d . . .

169

C22 C 0.18286(17) 0.2158(2) 0.10966(7) 0.0407(5) Uani 1 1 d . . . C23 C 0.0697(2) 0.2846(3) 0.09711(8) 0.0528(6) Uani 1 1 d . . . C24 C -0.0424(2) 0.2088(4) 0.09933(9) 0.0626(8) Uani 1 1 d . . . C25 C -0.0444(2) 0.0716(4) 0.11372(9) 0.0619(7) Uani 1 1 d . . . C26 C 0.06464(19) 0.0015(3) 0.12634(8) 0.0501(6) Uani 1 1 d . . . C27 C 0.17785(17) 0.0766(2) 0.12372(7) 0.0381(5) Uani 1 1 d . . . C28 C 0.3614(3) 0.4008(3) 0.09979(11) 0.0536(6) Uani 1 1 d . . . C30 C 0.63181(17) -0.1771(2) 0.05724(7) 0.0338(4) Uani 1 1 d . . . C31 C 0.6054(2) -0.3102(2) 0.07303(7) 0.0400(5) Uani 1 1 d . . . C32 C 0.6863(2) -0.4191(2) 0.06131(8) 0.0460(5) Uani 1 1 d . . . C33 C 0.7928(2) -0.3950(2) 0.03463(8) 0.0464(5) Uani 1 1 d . . . C34 C 0.8201(2) -0.2624(2) 0.01845(8) 0.0428(5) Uani 1 1 d . . . C35 C 0.73840(17) -0.1533(2) 0.02935(7) 0.0349(4) Uani 1 1 d . . . C40 C 0.63455(17) 0.0603(2) 0.03613(6) 0.0330(4) Uani 1 1 d . . . C41 C 0.6076(2) 0.1978(2) 0.02506(7) 0.0393(5) Uani 1 1 d . . . C42 C 0.6866(2) 0.2678(2) -0.00571(8) 0.0479(5) Uani 1 1 d . . . C43 C 0.7910(2) 0.2025(3) -0.02467(8) 0.0503(6) Uani 1 1 d . . . C44 C 0.8182(2) 0.0650(2) -0.01434(7) 0.0443(5) Uani 1 1 d . . . C45 C 0.73904(17) -0.0064(2) 0.01556(7) 0.0358(4) Uani 1 1 d . . . O1 O 0.38086(14) -0.20724(18) 0.19636(6) 0.0563(4) Uani 1 1 d D . . C50A C 0.2706(6) -0.2287(7) 0.2278(2) 0.0604(11) Uiso 0.45 1 d PD A 1 H50A H 0.2531 -0.1437 0.2462 0.072 Uiso 0.45 1 calc PR A 1 H50B H 0.1937 -0.2543 0.2098 0.072 Uiso 0.45 1 calc PR A 1 C51A C 0.3111(6) -0.3421(8) 0.2577(3) 0.0566(15) Uiso 0.45 1 d PD A 1 H51A H 0.2617 -0.4269 0.2500 0.068 Uiso 0.45 1 calc PR A 1 H51B H 0.2947 -0.3176 0.2906 0.068 Uiso 0.45 1 calc PR A 1 C52A C 0.4530(6) -0.3719(9) 0.2516(3) 0.0470(14) Uiso 0.45 1 d P A 1 H52A H 0.5047 -0.3274 0.2764 0.056 Uiso 0.45 1 calc PR A 1 H52B H 0.4706 -0.4732 0.2511 0.056 Uiso 0.45 1 calc PR A 1 C53A C 0.4743(8) -0.3089(10) 0.2070(4) 0.0550(10) Uiso 0.45 1 d PD A 1 H53A H 0.5590 -0.2646 0.2071 0.066 Uiso 0.45 1 calc PR A 1 H53B H 0.4732 -0.3819 0.1827 0.066 Uiso 0.45 1 calc PR A 1 C50B C 0.2671(9) -0.2668(19) 0.2135(6) 0.0604(11) Uiso 0.30 1 d PD A 2 H50B H 0.2104 -0.2942 0.1875 0.072 Uiso 0.30 1 calc PR A 2 H50C H 0.2220 -0.1993 0.2335 0.072 Uiso 0.30 1 calc PR A 2 C51B C 0.3083(8) -0.3980(10) 0.2425(3) 0.052(2) Uiso 0.30 1 d PD A 2 H51C H 0.2863 -0.3844 0.2756 0.063 Uiso 0.30 1 calc PR A 2 H51D H 0.2626 -0.4813 0.2309 0.063 Uiso 0.30 1 calc PR A 2 C52B C 0.4363(11) -0.4180(13) 0.2387(5) 0.076(3) Uiso 0.30 1 d P A 2 H52C H 0.4560 -0.5161 0.2309 0.091 Uiso 0.30 1 calc PR A 2 H52D H 0.4812 -0.3924 0.2679 0.091 Uiso 0.30 1 calc PR A 2 C53B C 0.4711(11) -0.3204(14) 0.1991(6) 0.0550(10) Uiso 0.30 1 d PD A 2 H53C H 0.5572 -0.2826 0.2045 0.066 Uiso 0.30 1 calc PR A 2 H53D H 0.4711 -0.3724 0.1693 0.066 Uiso 0.30 1 calc PR A 2 C50C C 0.2760(10) -0.275(2) 0.2155(6) 0.0604(11) Uiso 0.25 1 d PD A 3 H50D H 0.2662 -0.3706 0.2030 0.072 Uiso 0.25 1 calc PR A 3

170

H50E H 0.1968 -0.2221 0.2100 0.072 Uiso 0.25 1 calc PR A 3 C51C C 0.3126(10) -0.2764(14) 0.2656(4) 0.059(3) Uiso 0.25 1 d PD A 3 H51E H 0.3114 -0.1826 0.2799 0.071 Uiso 0.25 1 calc PR A 3 H51F H 0.2618 -0.3425 0.2842 0.071 Uiso 0.25 1 calc PR A 3 C52C C 0.4388(17) -0.3260(19) 0.2568(6) 0.089(6) Uiso 0.25 1 d P A 3 H52E H 0.4940 -0.2957 0.2829 0.107 Uiso 0.25 1 calc PR A 3 H52F H 0.4368 -0.4291 0.2572 0.107 Uiso 0.25 1 calc PR A 3 C53C C 0.4952(10) -0.2840(14) 0.2153(5) 0.0550(10) Uiso 0.25 1 d PD A 3 H53E H 0.5198 -0.3638 0.1955 0.066 Uiso 0.25 1 calc PR A 3 H53F H 0.5687 -0.2218 0.2206 0.066 Uiso 0.25 1 calc PR A 3 H1N H 0.457(2) -0.020(3) 0.2137(8) 0.049(6) Uiso 1 1 d . . . H2N H 0.325(2) -0.053(2) 0.1435(8) 0.039(6) Uiso 1 1 d . . . H1A H 0.5634(18) 0.205(2) 0.1192(7) 0.031(5) Uiso 1 1 d . . . H2A H 0.6714(19) -0.008(2) 0.1291(7) 0.036(5) Uiso 1 1 d . . . H2B H 0.5385(18) -0.088(2) 0.1368(7) 0.030(5) Uiso 1 1 d . . . H3A H 0.4707(18) -0.0460(19) 0.0577(7) 0.030(5) Uiso 1 1 d . . . H13 H 0.712(2) 0.371(2) 0.2939(8) 0.049(6) Uiso 1 1 d . . . H14 H 0.676(2) 0.276(3) 0.3700(9) 0.058(7) Uiso 1 1 d . . . H15 H 0.554(2) 0.073(2) 0.3775(9) 0.055(7) Uiso 1 1 d . . . H16 H 0.461(2) -0.038(2) 0.3110(8) 0.046(6) Uiso 1 1 d . . . H18A H 0.693(3) 0.451(3) 0.2041(11) 0.076(9) Uiso 1 1 d . . . H18B H 0.785(4) 0.340(4) 0.1842(13) 0.109(12) Uiso 1 1 d . . . H18C H 0.671(3) 0.390(4) 0.1553(14) 0.110(12) Uiso 1 1 d . . . H23 H 0.0775(18) 0.379(2) 0.0890(7) 0.032(5) Uiso 1 1 d . . . H24 H -0.119(3) 0.256(3) 0.0906(10) 0.071(8) Uiso 1 1 d . . . H25 H -0.131(3) 0.016(3) 0.1146(11) 0.087(9) Uiso 1 1 d . . . H26 H 0.064(3) -0.100(3) 0.1365(10) 0.069(8) Uiso 1 1 d . . . H28A H 0.350(3) 0.420(4) 0.0649(14) 0.103(11) Uiso 1 1 d . . . H28B H 0.316(3) 0.476(3) 0.1153(11) 0.085(10) Uiso 1 1 d . . . H28C H 0.446(3) 0.414(3) 0.1082(10) 0.069(8) Uiso 1 1 d . . . H31 H 0.530(2) -0.326(2) 0.0931(9) 0.051(6) Uiso 1 1 d . . . H32 H 0.665(2) -0.512(3) 0.0716(9) 0.057(7) Uiso 1 1 d . . . H33 H 0.847(2) -0.473(3) 0.0275(9) 0.057(7) Uiso 1 1 d . . . H34 H 0.888(2) -0.245(3) -0.0016(9) 0.057(7) Uiso 1 1 d . . . H41 H 0.532(2) 0.245(2) 0.0367(8) 0.040(6) Uiso 1 1 d . . . H42 H 0.668(2) 0.360(3) -0.0135(8) 0.048(6) Uiso 1 1 d . . . H43 H 0.844(2) 0.253(2) -0.0462(9) 0.051(6) Uiso 1 1 d . . . H44 H 0.888(2) 0.017(2) -0.0291(9) 0.051(6) Uiso 1 1 d . . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13

171

_atom_site_aniso_U_12 N1 0.0304(8) 0.0422(9) 0.0303(9) -0.0010(7) -0.0024(6) -0.0072(7) N2 0.0238(7) 0.0427(10) 0.0359(10) -0.0023(7) -0.0008(6) -0.0042(7) C1 0.0239(8) 0.0387(10) 0.0302(10) 0.0005(8) -0.0005(7) -0.0060(7) C2 0.0238(8) 0.0412(10) 0.0297(10) 0.0013(8) -0.0011(7) -0.0033(7) C3 0.0266(9) 0.0409(10) 0.0295(11) -0.0009(8) -0.0043(7) -0.0042(7) C10 0.0231(8) 0.0399(10) 0.0301(10) 0.0000(7) 0.0001(7) -0.0018(7) C11 0.0263(8) 0.0434(11) 0.0324(11) -0.0029(8) -0.0024(7) -0.0032(8) C12 0.0255(8) 0.0426(10) 0.0341(11) -0.0038(8) -0.0033(7) 0.0029(7) C13 0.0366(10) 0.0451(12) 0.0441(13) -0.0078(9) -0.0079(8) -0.0017(9) C14 0.0451(11) 0.0559(13) 0.0350(13) -0.0090(10) -0.0113(9) 0.0052(10) C15 0.0411(11) 0.0558(13) 0.0313(12) 0.0003(9) -0.0038(8) 0.0092(9) C16 0.0338(10) 0.0453(11) 0.0353(12) 0.0019(8) -0.0012(8) 0.0026(9) C17 0.0238(8) 0.0430(10) 0.0298(10) -0.0033(8) -0.0027(7) 0.0051(7) C18 0.0520(13) 0.0527(14) 0.0436(15) -0.0031(11) -0.0018(10) -0.0208(11) C20 0.0261(8) 0.0416(10) 0.0255(10) -0.0033(7) -0.0014(7) -0.0032(7) C21 0.0342(9) 0.0471(11) 0.0311(11) -0.0024(8) -0.0012(8) 0.0023(8) C22 0.0293(9) 0.0633(14) 0.0296(11) -0.0083(9) -0.0004(7) 0.0068(9) C23 0.0426(12) 0.0777(18) 0.0380(14) -0.0049(12) -0.0018(9) 0.0185(12) C24 0.0267(11) 0.117(2) 0.0443(15) -0.0070(14) -0.0016(9) 0.0182(13) C25 0.0286(11) 0.107(2) 0.0497(16) -0.0046(14) 0.0015(9) -0.0043(12) C26 0.0276(10) 0.0798(17) 0.0430(14) -0.0095(11) 0.0033(8) -0.0089(10) C27 0.0256(9) 0.0596(13) 0.0292(11) -0.0075(9) 0.0003(7) -0.0011(8) C28 0.0538(14) 0.0461(13) 0.0609(17) 0.0062(11) -0.0014(12) 0.0042(11) C30 0.0306(9) 0.0437(11) 0.0270(10) -0.0037(8) -0.0057(7) -0.0043(8) C31 0.0425(11) 0.0437(11) 0.0338(12) -0.0013(9) -0.0023(8) -0.0070(9) C32 0.0569(13) 0.0400(11) 0.0408(13) -0.0021(9) -0.0073(10) -0.0016(10) C33 0.0491(12) 0.0491(13) 0.0409(13) -0.0113(10) -0.0065(9) 0.0076(10) C34 0.0380(10) 0.0585(13) 0.0320(12) -0.0091(9) -0.0001(8) 0.0023(9) C35 0.0323(9) 0.0467(11) 0.0255(10) -0.0039(8) -0.0050(7) -0.0034(8) C40 0.0336(9) 0.0432(10) 0.0220(10) -0.0026(7) -0.0062(7) -0.0062(8) C41 0.0467(11) 0.0435(11) 0.0277(11) -0.0013(8) -0.0073(8) -0.0045(9) C42 0.0680(15) 0.0432(12) 0.0325(12) 0.0034(9) -0.0098(10) -0.0120(11) C43 0.0594(14) 0.0599(14) 0.0315(13) 0.0032(10) 0.0026(10) -0.0222(11) C44 0.0416(11) 0.0604(14) 0.0308(12) -0.0025(9) 0.0019(8) -0.0107(10) C45 0.0341(9) 0.0486(11) 0.0247(10) -0.0034(8) -0.0048(7) -0.0064(8) O1 0.0459(8) 0.0594(10) 0.0636(12) 0.0123(8) 0.0021(7) -0.0138(7)

172

; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag N1 C17 1.377(2) . ? N1 C10 1.389(2) . ? N1 H1N 0.93(2) . ? N2 C27 1.382(2) . ? N2 C20 1.385(2) . ? N2 H2N 0.92(2) . ? C1 C10 1.504(3) . ? C1 C20 1.516(2) . ? C1 C2 1.538(3) . ? C1 H1A 0.97(2) . ? C2 C3 1.545(3) . ? C2 H2A 1.03(2) . ? C2 H2B 1.00(2) . ? C3 C40 1.515(3) . ? C3 C30 1.517(3) . ? C3 H3A 1.023(19) . ? C10 C11 1.372(3) . ? C11 C12 1.437(3) . ? C11 C18 1.497(3) . ? C12 C17 1.407(3) . ? C12 C13 1.408(3) . ? C13 C14 1.374(3) . ? C13 H13 0.94(2) . ? C14 C15 1.397(3) . ? C14 H14 0.99(3) . ? C15 C16 1.381(3) . ? C15 H15 0.99(3) . ? C16 C17 1.396(3) . ? C16 H16 1.00(2) . ? C18 H18A 0.93(3) . ? C18 H18B 1.00(4) . ? C18 H18C 0.97(4) . ? C20 C21 1.367(3) . ? C21 C22 1.447(3) . ? C21 C28 1.486(3) . ? C22 C27 1.396(3) . ? C22 C23 1.409(3) . ? C23 C24 1.391(4) . ?

173

C23 H23 0.94(2) . ? C24 C25 1.381(4) . ? C24 H24 0.95(3) . ? C25 C26 1.379(4) . ? C25 H25 1.06(3) . ? C26 C27 1.399(3) . ? C26 H26 1.02(3) . ? C28 H28A 1.02(4) . ? C28 H28B 0.97(3) . ? C28 H28C 0.93(3) . ? C30 C31 1.385(3) . ? C30 C35 1.407(3) . ? C31 C32 1.394(3) . ? C31 H31 1.00(2) . ? C32 C33 1.387(3) . ? C32 H32 0.97(3) . ? C33 C34 1.386(3) . ? C33 H33 0.97(3) . ? C34 C35 1.394(3) . ? C34 H34 0.94(3) . ? C35 C45 1.464(3) . ? C40 C41 1.386(3) . ? C40 C45 1.411(3) . ? C41 C42 1.394(3) . ? C41 H41 0.98(2) . ? C42 C43 1.385(3) . ? C42 H42 0.94(2) . ? C43 C44 1.382(3) . ? C43 H43 0.97(2) . ? C44 C45 1.386(3) . ? C44 H44 0.98(2) . ? O1 C50C 1.401(11) . ? O1 C53A 1.419(8) . ? O1 C50B 1.423(9) . ? O1 C53B 1.447(10) . ? O1 C50A 1.495(6) . ? O1 C53C 1.511(10) . ? C50A C51A 1.448(8) . ? C50A H50A 0.9900 . ? C50A H50B 0.9900 . ? C51A C52A 1.537(9) . ? C51A H51A 0.9900 . ? C51A H51B 0.9900 . ? C52A C53A 1.436(15) . ? C52A H52A 0.9900 . ? C52A H52B 0.9900 . ?

174

C53A H53A 0.9900 . ? C53A H53B 0.9900 . ? C50B C51B 1.569(13) . ? C50B H50B 0.9900 . ? C50B H50C 0.9900 . ? C51B C52B 1.371(14) . ? C51B H51C 0.9900 . ? C51B H51D 0.9900 . ? C52B C53B 1.52(2) . ? C52B H52C 0.9900 . ? C52B H52D 0.9900 . ? C53B H53C 0.9900 . ? C53B H53D 0.9900 . ? C50C C51C 1.486(16) . ? C50C H50D 0.9900 . ? C50C H50E 0.9900 . ? C51C C52C 1.44(2) . ? C51C H51E 0.9900 . ? C51C H51F 0.9900 . ? C52C C53C 1.40(2) . ? C52C H52E 0.9900 . ? C52C H52F 0.9900 . ? C53C H53E 0.9900 . ? C53C H53F 0.9900 . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag C17 N1 C10 109.09(16) . . ? C17 N1 H1N 125.7(15) . . ? C10 N1 H1N 125.0(15) . . ? C27 N2 C20 108.74(17) . . ? C27 N2 H2N 126.3(13) . . ? C20 N2 H2N 125.0(13) . . ? C10 C1 C20 111.43(15) . . ? C10 C1 C2 110.46(15) . . ? C20 C1 C2 113.12(15) . . ? C10 C1 H1A 108.0(12) . . ? C20 C1 H1A 106.1(11) . . ? C2 C1 H1A 107.4(11) . . ? C1 C2 C3 116.76(16) . . ?

175

C1 C2 H2A 106.6(11) . . ? C3 C2 H2A 109.6(12) . . ? C1 C2 H2B 110.4(11) . . ? C3 C2 H2B 107.3(11) . . ? H2A C2 H2B 105.6(16) . . ? C40 C3 C30 102.05(15) . . ? C40 C3 C2 113.90(15) . . ? C30 C3 C2 108.53(15) . . ? C40 C3 H3A 110.8(11) . . ? C30 C3 H3A 111.4(11) . . ? C2 C3 H3A 109.9(11) . . ? C11 C10 N1 109.24(17) . . ? C11 C10 C1 130.16(17) . . ? N1 C10 C1 120.60(16) . . ? C10 C11 C12 106.78(17) . . ? C10 C11 C18 127.6(2) . . ? C12 C11 C18 125.61(18) . . ? C17 C12 C13 118.46(18) . . ? C17 C12 C11 107.36(16) . . ? C13 C12 C11 134.19(19) . . ? C14 C13 C12 119.2(2) . . ? C14 C13 H13 123.9(15) . . ? C12 C13 H13 116.8(15) . . ? C13 C14 C15 121.2(2) . . ? C13 C14 H14 120.5(15) . . ? C15 C14 H14 118.3(15) . . ? C16 C15 C14 121.5(2) . . ? C16 C15 H15 119.8(15) . . ? C14 C15 H15 118.6(14) . . ? C15 C16 C17 117.1(2) . . ? C15 C16 H16 121.3(13) . . ? C17 C16 H16 121.6(13) . . ? N1 C17 C16 129.89(18) . . ? N1 C17 C12 107.53(16) . . ? C16 C17 C12 122.57(18) . . ? C11 C18 H18A 114.0(18) . . ? C11 C18 H18B 110(2) . . ? H18A C18 H18B 107(3) . . ? C11 C18 H18C 116(2) . . ? H18A C18 H18C 108(3) . . ? H18B C18 H18C 102(3) . . ? C21 C20 N2 110.01(16) . . ? C21 C20 C1 129.77(17) . . ? N2 C20 C1 120.10(16) . . ? C20 C21 C22 105.94(18) . . ? C20 C21 C28 128.56(19) . . ?

176

C22 C21 C28 125.5(2) . . ? C27 C22 C23 119.2(2) . . ? C27 C22 C21 107.78(17) . . ? C23 C22 C21 133.0(2) . . ? C24 C23 C22 117.6(3) . . ? C24 C23 H23 126.3(13) . . ? C22 C23 H23 116.1(13) . . ? C25 C24 C23 121.9(2) . . ? C25 C24 H24 121.0(17) . . ? C23 C24 H24 117.1(17) . . ? C26 C25 C24 121.9(2) . . ? C26 C25 H25 117.7(17) . . ? C24 C25 H25 120.3(17) . . ? C25 C26 C27 116.5(3) . . ? C25 C26 H26 122.2(16) . . ? C27 C26 H26 121.3(16) . . ? N2 C27 C22 107.52(17) . . ? N2 C27 C26 129.6(2) . . ? C22 C27 C26 122.9(2) . . ? C21 C28 H28A 110.4(19) . . ? C21 C28 H28B 113.8(18) . . ? H28A C28 H28B 105(3) . . ? C21 C28 H28C 113.0(17) . . ? H28A C28 H28C 109(3) . . ? H28B C28 H28C 105(2) . . ? C31 C30 C35 120.10(18) . . ? C31 C30 C3 129.57(17) . . ? C35 C30 C3 110.27(16) . . ? C30 C31 C32 119.1(2) . . ? C30 C31 H31 119.4(14) . . ? C32 C31 H31 121.5(14) . . ? C33 C32 C31 120.7(2) . . ? C33 C32 H32 121.2(15) . . ? C31 C32 H32 118.1(15) . . ? C34 C33 C32 120.8(2) . . ? C34 C33 H33 120.8(15) . . ? C32 C33 H33 118.4(15) . . ? C33 C34 C35 118.8(2) . . ? C33 C34 H34 122.1(15) . . ? C35 C34 H34 118.9(15) . . ? C34 C35 C30 120.43(19) . . ? C34 C35 C45 131.11(19) . . ? C30 C35 C45 108.44(17) . . ? C41 C40 C45 119.71(18) . . ? C41 C40 C3 130.07(18) . . ? C45 C40 C3 110.17(17) . . ?

177

C40 C41 C42 118.8(2) . . ? C40 C41 H41 122.1(12) . . ? C42 C41 H41 119.0(12) . . ? C43 C42 C41 121.0(2) . . ? C43 C42 H42 120.3(14) . . ? C41 C42 H42 118.7(14) . . ? C44 C43 C42 120.8(2) . . ? C44 C43 H43 119.5(14) . . ? C42 C43 H43 119.7(14) . . ? C43 C44 C45 118.7(2) . . ? C43 C44 H44 121.2(14) . . ? C45 C44 H44 120.0(14) . . ? C44 C45 C40 121.0(2) . . ? C44 C45 C35 130.40(19) . . ? C40 C45 C35 108.53(17) . . ? C50C O1 C53A 98.4(9) . . ? C50C O1 C50B 5.4(10) . . ? C53A O1 C50B 103.7(8) . . ? C50C O1 C53B 98.8(11) . . ? C53A O1 C53B 10.2(9) . . ? C50B O1 C53B 103.8(8) . . ? C50C O1 C50A 22.5(11) . . ? C53A O1 C50A 108.6(6) . . ? C50B O1 C50A 21.5(9) . . ? C53B O1 C50A 112.4(7) . . ? C50C O1 C53C 105.3(8) . . ? C53A O1 C53C 15.3(7) . . ? C50B O1 C53C 110.7(8) . . ? C53B O1 C53C 24.6(6) . . ? C50A O1 C53C 109.8(6) . . ? C51A C50A O1 103.6(5) . . ? C51A C50A H50A 111.0 . . ? O1 C50A H50A 111.0 . . ? C51A C50A H50B 111.0 . . ? O1 C50A H50B 111.0 . . ? H50A C50A H50B 109.0 . . ? C50A C51A C52A 110.8(5) . . ? C50A C51A H51A 109.5 . . ? C52A C51A H51A 109.5 . . ? C50A C51A H51B 109.5 . . ? C52A C51A H51B 109.5 . . ? H51A C51A H51B 108.1 . . ? C53A C52A C51A 100.7(6) . . ? C53A C52A H52A 111.6 . . ? C51A C52A H52A 111.6 . . ? C53A C52A H52B 111.6 . . ?

178

C51A C52A H52B 111.6 . . ? H52A C52A H52B 109.4 . . ? O1 C53A C52A 111.5(7) . . ? O1 C53A H53A 109.3 . . ? C52A C53A H53A 109.3 . . ? O1 C53A H53B 109.3 . . ? C52A C53A H53B 109.3 . . ? H53A C53A H53B 108.0 . . ? O1 C50B C51B 106.0(7) . . ? O1 C50B H50B 110.5 . . ? C51B C50B H50B 110.5 . . ? O1 C50B H50C 110.5 . . ? C51B C50B H50C 110.5 . . ? H50B C50B H50C 108.7 . . ? C52B C51B C50B 109.8(8) . . ? C52B C51B H51C 109.7 . . ? C50B C51B H51C 109.7 . . ? C52B C51B H51D 109.7 . . ? C50B C51B H51D 109.7 . . ? H51C C51B H51D 108.2 . . ? C51B C52B C53B 102.7(9) . . ? C51B C52B H52C 111.2 . . ? C53B C52B H52C 111.2 . . ? C51B C52B H52D 111.2 . . ? C53B C52B H52D 111.2 . . ? H52C C52B H52D 109.1 . . ? O1 C53B C52B 109.8(10) . . ? O1 C53B H53C 109.7 . . ? C52B C53B H53C 109.7 . . ? O1 C53B H53D 109.7 . . ? C52B C53B H53D 109.7 . . ? H53C C53B H53D 108.2 . . ? O1 C50C C51C 100.7(11) . . ? O1 C50C H50D 111.6 . . ? C51C C50C H50D 111.6 . . ? O1 C50C H50E 111.6 . . ? C51C C50C H50E 111.6 . . ? H50D C50C H50E 109.4 . . ? C52C C51C C50C 93.7(11) . . ? C52C C51C H51E 113.0 . . ? C50C C51C H51E 113.0 . . ? C52C C51C H51F 113.0 . . ? C50C C51C H51F 113.0 . . ? H51E C51C H51F 110.4 . . ? C53C C52C C51C 117.3(14) . . ? C53C C52C H52E 108.0 . . ?

179

C51C C52C H52E 108.0 . . ? C53C C52C H52F 108.0 . . ? C51C C52C H52F 108.0 . . ? H52E C52C H52F 107.2 . . ? C52C C53C O1 95.8(10) . . ? C52C C53C H53E 112.6 . . ? O1 C53C H53E 112.6 . . ? C52C C53C H53F 112.6 . . ? O1 C53C H53F 112.6 . . ? H53E C53C H53F 110.1 . . ?

_diffrn_measured_fraction_theta_max 0.952 _diffrn_reflns_theta_full 25.99 _diffrn_measured_fraction_theta_full 0.952 _refine_diff_density_max 0.350 _refine_diff_density_min -0.410 _refine_diff_density_rms 0.041

180

CIF File for (HFDI)Zr(NEt2)2(THF)

_audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C45 H54 N4 O Zr' _chemical_formula_sum 'C45 H54 N4 O Zr' _chemical_formula_weight 758.14 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source 'C' 'C' 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'H' 'H' 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'N' 'N' 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'O' 'O' 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'Zr' 'Zr' -2.9673 0.5597 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting ? _symmetry_space_group_name_H-M ? loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y-1/2, z-1/2'

_cell_length_a 21.814(3) _cell_length_b 18.146(2) _cell_length_c 27.820(3) _cell_angle_alpha 90.00 _cell_angle_beta 110.216(2) _cell_angle_gamma 90.00

181

_cell_volume 10334(2) _cell_formula_units_Z 8 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ?

_exptl_crystal_description „cubic‟ _exptl_crystal_colour „pale yellow‟ _exptl_crystal_size_max .30 _exptl_crystal_size_mid .30 _exptl_crystal_size_min .25 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 0.975 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 3200 _exptl_absorpt_coefficient_mu 0.242 _exptl_absorpt_correction_type ? _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details ?

_exptl_special_details ; ? ;

_diffrn_ambient_temperature 140(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type ? _diffrn_measurement_method ? _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 93808 _diffrn_reflns_av_R_equivalents 0.0325 _diffrn_reflns_av_sigmaI/netI 0.0328 _diffrn_reflns_limit_h_min -30 _diffrn_reflns_limit_h_max 29 _diffrn_reflns_limit_k_min -25 _diffrn_reflns_limit_k_max 25

182

_diffrn_reflns_limit_l_min -40 _diffrn_reflns_limit_l_max 38 _diffrn_reflns_theta_min 0.99 _diffrn_reflns_theta_max 31.74 _reflns_number_total 32334 _reflns_number_gt 26138 _reflns_threshold_expression >2sigma(I)

_computing_data_collection ? _computing_cell_refinement ? _computing_data_reduction ? _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ? _computing_publication_material ?

_refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.1000P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment mixed _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 32334 _refine_ls_number_parameters 1617 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1011 _refine_ls_R_factor_gt 0.0818 _refine_ls_wR_factor_ref 0.2307 _refine_ls_wR_factor_gt 0.2222 _refine_ls_goodness_of_fit_ref 1.634

183

_refine_ls_restrained_S_all 1.634 _refine_ls_shift/su_max 0.445 _refine_ls_shift/su_mean 0.017 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Zr1 Zr 0.449025(11) 0.285304(13) 0.175076(9) 0.01680(7) Uani 1 1 d . . . Zr2 Zr 0.049123(11) 0.743721(13) 0.321298(9) 0.01618(7) Uani 1 1 d . . . N1 N 0.52731(10) 0.21692(13) 0.16538(9) 0.0207(4) Uani 1 1 d . . . N2 N 0.52351(10) 0.37223(12) 0.19357(9) 0.0195(4) Uani 1 1 d . . . N3 N 0.38096(11) 0.32197(13) 0.11025(9) 0.0245(5) Uani 1 1 d . . . N4 N 0.41819(11) 0.30345(12) 0.23537(9) 0.0211(4) Uani 1 1 d . . . N1A N -0.02960(10) 0.81379(12) 0.32966(8) 0.0186(4) Uani 1 1 d . . . N2A N -0.02570(10) 0.65743(12) 0.30286(8) 0.0184(4) Uani 1 1 d . . . N3A N 0.11699(11) 0.70603(13) 0.38606(9) 0.0233(5) Uani 1 1 d . . . N4A N 0.07979(11) 0.72495(13) 0.26129(9) 0.0205(4) Uani 1 1 d . . . O1 O 0.40937(9) 0.16887(10) 0.17540(8) 0.0238(4) Uani 1 1 d . . . O2 O 0.31531(12) 0.61609(14) 0.91921(10) 0.0408(6) Uani 1 1 d . . . O3 O 0.18534(12) 0.35205(14) 0.58523(10) 0.0388(5) Uani 1 1 d . . . O4 O 0.26460(15) 0.50498(16) 0.01341(14) 0.0602(8) Uani 1 1 d . . . O5 O 0.9784(4) 0.2565(4) 0.4371(3) 0.0609(17) Uiso 0.50 1 d P A 1 O5A O 0.9715(3) 0.2359(3) 0.4163(2) 0.0441(13) Uiso 0.50 1 d P A 3 O6 O 0.4744(3) 0.2935(3) 0.4177(2) 0.1227(18) Uiso 1 1 d . . . O1A O 0.09242(9) 0.85935(10) 0.32413(7) 0.0211(4) Uani 1 1 d . . . C1 C 0.61189(12) 0.28034(14) 0.23813(10) 0.0184(5) Uani 1 1 d . . . C2 C 0.58486(13) 0.25562(15) 0.28092(11) 0.0213(5) Uani 1 1 d . . . C3 C 0.63861(13) 0.22954(16) 0.33047(11) 0.0222(5) Uani 1 1 d . . . C10 C 0.59313(12) 0.22747(14) 0.19365(10) 0.0178(5) Uani 1 1 d . . . C11 C 0.63297(12) 0.18582(14) 0.17528(10) 0.0198(5) Uani 1 1 d . . . C12 C 0.59010(13) 0.14560(16) 0.13255(11) 0.0235(5) Uani 1 1 d . . . C13 C 0.60078(17) 0.0937(2) 0.09873(13) 0.0349(7) Uani 1 1 d . . . C14 C 0.54712(19) 0.0624(2) 0.06207(14) 0.0474(10) Uani 1 1 d . . . C15 C 0.4841(2) 0.0823(2) 0.05789(15) 0.0487(10) Uani 1 1 d . . . C16 C 0.47206(16) 0.1346(2) 0.08949(13) 0.0358(7) Uani 1 1 d . . .

184

C17 C 0.52582(13) 0.16617(15) 0.12740(11) 0.0237(5) Uani 1 1 d . . . C18 C 0.70593(15) 0.18161(19) 0.19504(13) 0.0268(6) Uani 1 1 d . . . C20 C 0.58967(12) 0.35727(14) 0.21907(10) 0.0189(5) Uani 1 1 d . . . C21 C 0.62891(13) 0.41779(14) 0.22106(11) 0.0210(5) Uani 1 1 d . . . C22 C 0.58535(13) 0.47569(14) 0.19491(10) 0.0211(5) Uani 1 1 d . . . C23 C 0.59490(15) 0.54795(16) 0.18142(12) 0.0268(6) Uani 1 1 d . . . C24 C 0.54130(16) 0.59019(16) 0.15415(12) 0.0298(6) Uani 1 1 d . . . C25 C 0.47834(16) 0.56186(16) 0.14126(12) 0.0294(6) Uani 1 1 d . . . C26 C 0.46695(14) 0.48989(16) 0.15334(11) 0.0249(5) Uani 1 1 d . . . C27 C 0.52134(12) 0.44591(14) 0.17953(10) 0.0201(5) Uani 1 1 d . . . C28 C 0.70174(14) 0.42331(18) 0.24542(14) 0.0290(6) Uani 1 1 d . . . C30 C 0.68093(13) 0.16694(15) 0.32297(10) 0.0219(5) Uani 1 1 d . . . C31 C 0.66183(17) 0.09900(17) 0.29968(12) 0.0303(6) Uani 1 1 d . . . C32 C 0.71065(18) 0.05045(18) 0.29723(14) 0.0345(7) Uani 1 1 d . . . C33 C 0.77609(17) 0.06922(18) 0.31806(14) 0.0351(7) Uani 1 1 d . . . C34 C 0.79520(16) 0.13692(18) 0.34185(12) 0.0306(6) Uani 1 1 d . . . C35 C 0.74723(14) 0.18575(16) 0.34399(11) 0.0241(5) Uani 1 1 d . . . C40 C 0.68896(14) 0.28698(15) 0.35674(10) 0.0230(5) Uani 1 1 d . . . C41 C 0.67989(17) 0.35782(18) 0.37271(12) 0.0317(7) Uani 1 1 d . . . C42 C 0.73473(19) 0.40103(19) 0.39761(12) 0.0376(8) Uani 1 1 d . . . C43 C 0.79632(19) 0.3744(2) 0.40609(13) 0.0389(8) Uani 1 1 d . . . C44 C 0.80683(16) 0.30383(19) 0.39052(12) 0.0311(6) Uani 1 1 d . . . C45 C 0.75232(14) 0.26074(16) 0.36552(11) 0.0245(5) Uani 1 1 d . . . C50 C 0.31722(14) 0.35714(17) 0.10090(12) 0.0281(6) Uani 1 1 d . . . C51 C 0.26013(16) 0.3204(2) 0.05948(15) 0.0375(8) Uani 1 1 d . . . C52 C 0.40044(14) 0.31401(18) 0.06478(11) 0.0286(6) Uani 1 1 d . . . C53 C 0.40605(16) 0.3868(2) 0.03913(13) 0.0330(7) Uani 1 1 d . . . C60 C 0.39916(14) 0.38009(16) 0.23872(12) 0.0262(6) Uani 1 1 d . . . C61 C 0.4461(2) 0.4235(2) 0.28364(16) 0.0400(8) Uani 1 1 d . . . C62 C 0.42052(14) 0.25729(16) 0.27871(11) 0.0239(5) Uani 1 1 d . . . C63 C 0.35445(17) 0.24404(19) 0.28392(15) 0.0322(7) Uani 1 1 d . . . C70 C 0.33850(14) 0.15728(17) 0.15410(13) 0.0282(6) Uani 1 1 d . . . C71 C 0.32814(16) 0.08121(17) 0.17323(15) 0.0347(7) Uani 1 1 d . . . C72 C 0.39047(16) 0.04068(16) 0.17576(14) 0.0314(6) Uani 1 1 d . . . C73 C 0.44199(14) 0.09939(15) 0.19787(12) 0.0268(6) Uani 1 1 d . . . C1A C -0.11230(12) 0.74958(13) 0.25652(10) 0.0167(5) Uani 1 1 d . . . C2A C -0.08473(13) 0.77416(16) 0.21459(10) 0.0204(5) Uani 1 1 d . . . C3A C -0.18764(14) 0.74548(14) 0.13850(10) 0.0225(5) Uani 1 1 d . . . C10A C -0.09501(12) 0.80286(14) 0.30092(10) 0.0175(5) Uani 1 1 d . . . C11A C -0.13580(12) 0.84385(14) 0.31844(10) 0.0200(5) Uani 1 1 d . . . C12A C -0.09396(13) 0.88531(14) 0.36087(10) 0.0202(5) Uani 1 1 d . . . C13A C -0.10550(16) 0.93824(17) 0.39345(11) 0.0269(6) Uani 1 1 d . . . C14A C -0.05232(18) 0.97125(18) 0.43010(12) 0.0322(7) Uani 1 1 d . . . C15A C 0.01094(17) 0.95218(18) 0.43539(12) 0.0318(7) Uani 1 1 d . . . C16A C 0.02398(14) 0.89825(16) 0.40435(11) 0.0254(6) Uani 1 1 d . . . C17A C -0.02871(12) 0.86542(14) 0.36679(10) 0.0195(5) Uani 1 1 d . . .

185

C18A C -0.20876(14) 0.84662(18) 0.29821(12) 0.0266(6) Uani 1 1 d . . . C20A C -0.09201(12) 0.67255(13) 0.27597(10) 0.0168(4) Uani 1 1 d . . . C21A C -0.13163(13) 0.61312(14) 0.27438(10) 0.0191(5) Uani 1 1 d . . . C22A C -0.08918(13) 0.55545(14) 0.30214(10) 0.0199(5) Uani 1 1 d . . . C23A C -0.10050(14) 0.48394(15) 0.31690(11) 0.0231(5) Uani 1 1 d . . . C24A C -0.04702(16) 0.44269(16) 0.34606(12) 0.0282(6) Uani 1 1 d . . . C25A C 0.01667(15) 0.46975(16) 0.35970(12) 0.0275(6) Uani 1 1 d . . . C26A C 0.02897(14) 0.54055(16) 0.34620(11) 0.0241(5) Uani 1 1 d . . . C27A C -0.02463(13) 0.58416(14) 0.31828(10) 0.0187(5) Uani 1 1 d . . . C28A C -0.20404(14) 0.60863(17) 0.24941(13) 0.0265(6) Uani 1 1 d . . . C30A C -0.17916(13) 0.86532(15) 0.17284(10) 0.0216(5) Uani 1 1 d . . . C31A C -0.15986(15) 0.93301(16) 0.19638(12) 0.0267(6) Uani 1 1 d . . . C32A C -0.20835(18) 0.98258(17) 0.19781(14) 0.0347(7) Uani 1 1 d . . . C33A C -0.27383(17) 0.96465(18) 0.17626(14) 0.0347(7) Uani 1 1 d . . . C34A C -0.29316(15) 0.89743(18) 0.15186(12) 0.0303(6) Uani 1 1 d . . . C35A C -0.24535(13) 0.84746(15) 0.15085(10) 0.0231(5) Uani 1 1 d . . . C40A C -0.13718(13) 0.80261(14) 0.16546(10) 0.0203(5) Uani 1 1 d . . . C41A C -0.17923(17) 0.67462(17) 0.12222(11) 0.0300(6) Uani 1 1 d . . . C42A C -0.2339(2) 0.63276(19) 0.09695(13) 0.0405(8) Uani 1 1 d . . . C43A C -0.2962(2) 0.6598(2) 0.08857(13) 0.0416(8) Uani 1 1 d . . . C44A C -0.30586(17) 0.7304(2) 0.10427(12) 0.0345(7) Uani 1 1 d . . . C45A C -0.25066(14) 0.77262(16) 0.12965(11) 0.0246(5) Uani 1 1 d . . . C50A C 0.10004(15) 0.71911(18) 0.43216(11) 0.0280(6) Uani 1 1 d . . . C51A C 0.09453(18) 0.6495(2) 0.46122(13) 0.0374(8) Uani 1 1 d . . . C52A C 0.17878(14) 0.66675(19) 0.39448(13) 0.0301(6) Uani 1 1 d . . . C53A C 0.23805(16) 0.7014(2) 0.43488(15) 0.0394(8) Uani 1 1 d . . . C60A C 0.08186(13) 0.77342(16) 0.21999(11) 0.0214(5) Uani 1 1 d . . . C61A C 0.15080(15) 0.79231(18) 0.22266(14) 0.0291(6) Uani 1 1 d . . . C62A C 0.09618(15) 0.64763(15) 0.25528(12) 0.0252(6) Uani 1 1 d . . . C63A C 0.0477(2) 0.6071(2) 0.21069(16) 0.0403(8) Uani 1 1 d . . . C70A C 0.16275(14) 0.87241(17) 0.35036(12) 0.0270(6) Uani 1 1 d . . . C71A C 0.17455(16) 0.94821(19) 0.33308(16) 0.0345(7) Uani 1 1 d . . . C72A C 0.11028(15) 0.98744(17) 0.32500(12) 0.0283(6) Uani 1 1 d . . . C73A C 0.06097(14) 0.92844(16) 0.29987(12) 0.0260(6) Uani 1 1 d . . . C80 C 0.35034(17) 0.6624(2) 0.89597(15) 0.0387(8) Uani 1 1 d . . . C81 C 0.42151(17) 0.6377(2) 0.91641(15) 0.0382(8) Uani 1 1 d . . . C82 C 0.41987(19) 0.5638(2) 0.94222(17) 0.0462(9) Uani 1 1 d . . . C83 C 0.34754(19) 0.5465(2) 0.92431(17) 0.0428(8) Uani 1 1 d . . . C90 C 0.15124(18) 0.3037(2) 0.60800(14) 0.0381(7) Uani 1 1 d . . . C91 C 0.07994(17) 0.3263(2) 0.58699(14) 0.0361(7) Uani 1 1 d . . . C92 C 0.08076(19) 0.4030(2) 0.56462(15) 0.0420(8) Uani 1 1 d . . . C93 C 0.15276(19) 0.4206(2) 0.58177(16) 0.0402(8) Uani 1 1 d . . . C100 C 0.3016(5) 0.5643(6) 0.0492(4) 0.051(3) Uiso 0.50 1 d P B 1 C200 C 0.3004(6) 0.5688(7) 0.0349(5) 0.053(3) Uiso 0.50 1 d P B 3 C101 C 0.2566(3) 0.6302(2) 0.02787(18) 0.0593(12) Uani 1 1 d . . . C102 C 0.1904(2) 0.5950(3) 0.02139(19) 0.0639(13) Uani 1 1 d . B .

186

C103 C 0.1974(2) 0.5181(3) 0.0005(2) 0.0631(12) Uani 1 1 d . B . C110 C 1.0336(2) 0.2787(3) 0.4298(2) 0.0705(15) Uani 1 1 d . . . C111 C 1.0888(2) 0.2348(2) 0.46529(15) 0.0447(9) Uani 1 1 d . A . C112 C 1.0557(3) 0.1627(3) 0.4704(3) 0.088(2) Uani 1 1 d . . . C113 C 0.9844(3) 0.1836(3) 0.4575(2) 0.0755(16) Uani 1 1 d . A . C120 C 0.5252(5) 0.3529(6) 0.4253(4) 0.156(4) Uiso 1 1 d . . . C121 C 0.5874(4) 0.3162(5) 0.4589(3) 0.112(2) Uiso 1 1 d . . . O7 O 0.2181(3) 0.3853(3) 0.4720(2) 0.1282(19) Uiso 1 1 d . . . C133 C 0.2065(4) 0.4699(4) 0.4558(3) 0.099(2) Uiso 1 1 d . . . C131 C 0.3068(3) 0.4495(4) 0.5243(2) 0.0818(16) Uiso 1 1 d . . . C132 C 0.2794(3) 0.4985(4) 0.4831(3) 0.0878(18) Uiso 1 1 d . . . C123 C 0.4985(4) 0.2429(5) 0.4558(3) 0.112(2) Uiso 1 1 d . . . C130 C 0.2917(4) 0.3872(5) 0.5014(3) 0.109(2) Uiso 1 1 d . . . C122 C 0.5702(6) 0.2424(7) 0.4655(4) 0.162(4) Uiso 1 1 d . . . H1A H -0.1564(14) 0.7508(15) 0.2419(11) 0.006(6) Uiso 1 1 d . . . H2A H -0.0521(17) 0.811(2) 0.2244(13) 0.029(9) Uiso 1 1 d . . . H1 H 0.6606(14) 0.2796(15) 0.2533(11) 0.009(7) Uiso 1 1 d . . . H22A H -0.1448(14) 0.4658(16) 0.3063(11) 0.014(7) Uiso 1 1 d . . . H2Y H 0.5479(18) 0.214(2) 0.2633(14) 0.033(9) Uiso 1 1 d . . . H2X H 0.5627(15) 0.3009(18) 0.2937(12) 0.022(8) Uiso 1 1 d . . . H26A H 0.0732(16) 0.5569(18) 0.3568(12) 0.021(8) Uiso 1 1 d . . . H2B H -0.0632(16) 0.7303(19) 0.2044(13) 0.024(8) Uiso 1 1 d . . . H16 H 0.4303(19) 0.146(2) 0.0877(14) 0.036(10) Uiso 1 1 d . . . H3A H -0.1154(15) 0.8176(17) 0.1412(12) 0.018(8) Uiso 1 1 d . . . H25A H 0.0541(17) 0.445(2) 0.3827(13) 0.029(9) Uiso 1 1 d . . . H14A H -0.056(2) 0.996(2) 0.4543(17) 0.053(13) Uiso 1 1 d . . . H15A H 0.0422(19) 0.975(2) 0.4606(15) 0.039(10) Uiso 1 1 d . . . H34A H -0.3340(18) 0.890(2) 0.1379(14) 0.031(9) Uiso 1 1 d . . . H31A H -0.1146(18) 0.944(2) 0.2096(13) 0.029(9) Uiso 1 1 d . . . H24A H -0.0545(19) 0.400(2) 0.3603(15) 0.042(11) Uiso 1 1 d . . . H25 H 0.4453(17) 0.595(2) 0.1263(13) 0.030(9) Uiso 1 1 d . . . H33A H -0.3047(19) 1.004(2) 0.1796(15) 0.044(11) Uiso 1 1 d . . . H13A H -0.1444(18) 0.951(2) 0.3904(13) 0.029(9) Uiso 1 1 d . . . H13 H 0.638(2) 0.076(2) 0.1045(15) 0.045(12) Uiso 1 1 d . . . H32 H 0.707(2) 0.012(2) 0.2871(16) 0.047(12) Uiso 1 1 d . . . H62A H 0.4534(16) 0.2752(19) 0.3104(13) 0.022(8) Uiso 1 1 d . . . H73B H 0.4804(15) 0.0954(16) 0.1870(11) 0.014(7) Uiso 1 1 d . . . H62B H 0.4436(17) 0.210(2) 0.2776(14) 0.029(9) Uiso 1 1 d . . . H70B H 0.3249(19) 0.159(2) 0.1143(16) 0.044(11) Uiso 1 1 d . . . H26 H 0.4215(15) 0.4703(17) 0.1417(12) 0.018(8) Uiso 1 1 d . . . H70A H 0.3216(19) 0.193(2) 0.1696(15) 0.039(10) Uiso 1 1 d . . . H51A H 0.265(2) 0.330(3) 0.0257(18) 0.059(13) Uiso 1 1 d . . . H60A H 0.3871(18) 0.406(2) 0.2030(14) 0.035(10) Uiso 1 1 d . . . H60B H 0.3546(18) 0.381(2) 0.2388(14) 0.034(10) Uiso 1 1 d . . . H50A H 0.3198(17) 0.413(2) 0.0880(13) 0.032(9) Uiso 1 1 d . . . H73A H 0.4563(17) 0.107(2) 0.2407(14) 0.033(9) Uiso 1 1 d . . .

187

H72X H 0.1028(15) 1.0036(18) 0.3571(13) 0.021(8) Uiso 1 1 d . . . H62X H 0.1431(18) 0.642(2) 0.2533(14) 0.035(10) Uiso 1 1 d . . . H73X H 0.0201(16) 0.9327(18) 0.3072(12) 0.020(8) Uiso 1 1 d . . . H53X H 0.2742(19) 0.679(2) 0.4348(14) 0.030(9) Uiso 1 1 d . . . H50X H 0.1400(18) 0.752(2) 0.4603(15) 0.034(10) Uiso 1 1 d . . . H61X H 0.1790(19) 0.818(2) 0.2588(15) 0.043(11) Uiso 1 1 d . . . H81A H 0.4477(16) 0.6693(19) 0.9382(13) 0.023(8) Uiso 1 1 d . . . H52Y H 0.1893(17) 0.665(2) 0.3601(14) 0.030(9) Uiso 1 1 d . . . H71X H 0.182(2) 0.942(2) 0.2980(16) 0.047(11) Uiso 1 1 d . . . H50Y H 0.0554(19) 0.743(2) 0.4214(14) 0.031(9) Uiso 1 1 d . . . H60Y H 0.053(2) 0.756(2) 0.1858(17) 0.046(11) Uiso 1 1 d . . . H52X H 0.1765(18) 0.616(2) 0.4093(14) 0.036(10) Uiso 1 1 d . . . H91A H 0.0505(18) 0.294(2) 0.5592(15) 0.037(10) Uiso 1 1 d . . . H16A H 0.0684(17) 0.8905(19) 0.4087(12) 0.022(8) Uiso 1 1 d . . . H83A H 0.339(2) 0.529(3) 0.9499(18) 0.056(14) Uiso 1 1 d . . . H73Y H 0.0539(14) 0.9242(17) 0.2642(12) 0.015(7) Uiso 1 1 d . . . H60X H 0.0574(16) 0.8175(19) 0.2229(13) 0.025(8) Uiso 1 1 d . . . H50B H 0.3053(16) 0.3553(19) 0.1336(13) 0.027(9) Uiso 1 1 d . . . H71Y H 0.190(2) 0.972(3) 0.3536(17) 0.051(14) Uiso 1 1 d . . . H71A H 0.289(2) 0.062(2) 0.1490(16) 0.055(13) Uiso 1 1 d . . . H80A H 0.347(2) 0.717(3) 0.9089(18) 0.060(14) Uiso 1 1 d . . . H63A H 0.361(2) 0.207(3) 0.3115(18) 0.060(14) Uiso 1 1 d . . . H53B H 0.3633(18) 0.414(2) 0.0282(13) 0.031(9) Uiso 1 1 d . . . H72A H 0.4059(18) -0.003(2) 0.2029(14) 0.034(10) Uiso 1 1 d . . . H42A H -0.233(2) 0.581(3) 0.0843(17) 0.059(13) Uiso 1 1 d . . . H53A H 0.4217(18) 0.381(2) 0.0155(15) 0.035(10) Uiso 1 1 d . . . H51X H 0.1371(16) 0.6291(18) 0.4789(12) 0.021(8) Uiso 1 1 d . . . H52A H 0.361(2) 0.282(3) 0.0353(18) 0.061(14) Uiso 1 1 d . . . H51B H 0.2501(16) 0.271(2) 0.0663(13) 0.021(8) Uiso 1 1 d . . . H70X H 0.1878(17) 0.836(2) 0.3324(14) 0.032(9) Uiso 1 1 d . . . H32A H -0.1921(19) 1.024(2) 0.2162(15) 0.043(11) Uiso 1 1 d . . . H61A H 0.488(2) 0.426(3) 0.2799(17) 0.061(14) Uiso 1 1 d . . . H3 H 0.6204(17) 0.211(2) 0.3534(14) 0.030(9) Uiso 1 1 d . . . H51Y H 0.0811(18) 0.663(2) 0.4896(15) 0.038(10) Uiso 1 1 d . . . H92A H 0.062(2) 0.400(3) 0.5250(19) 0.066(15) Uiso 1 1 d . . . H93A H 0.1651(18) 0.444(2) 0.6182(15) 0.037(10) Uiso 1 1 d . . . H93B H 0.167(2) 0.449(3) 0.5604(17) 0.053(13) Uiso 1 1 d . . . H70Y H 0.1727(17) 0.870(2) 0.3869(14) 0.029(9) Uiso 1 1 d . . . H63B H 0.339(2) 0.292(3) 0.2909(16) 0.050(12) Uiso 1 1 d . . . H23 H 0.6289(17) 0.566(2) 0.1909(13) 0.025(9) Uiso 1 1 d . . . H72B H 0.3870(18) 0.028(2) 0.1394(15) 0.036(10) Uiso 1 1 d . . . H62Y H 0.1017(18) 0.621(2) 0.2874(15) 0.036(10) Uiso 1 1 d . . . H90A H 0.1572(18) 0.251(2) 0.5949(14) 0.030(9) Uiso 1 1 d . . . H41 H 0.641(2) 0.373(2) 0.3712(16) 0.048(12) Uiso 1 1 d . . . H61Z H 0.173(2) 0.752(3) 0.2238(18) 0.054(13) Uiso 1 1 d . . . H44 H 0.8461(18) 0.289(2) 0.3958(14) 0.030(10) Uiso 1 1 d . . .

188

H31 H 0.6188(18) 0.086(2) 0.2908(13) 0.028(9) Uiso 1 1 d . . . H34 H 0.8406(19) 0.144(2) 0.3572(15) 0.041(11) Uiso 1 1 d . . . H53Y H 0.243(2) 0.697(3) 0.4720(18) 0.056(13) Uiso 1 1 d . . . H52B H 0.447(2) 0.277(2) 0.0776(17) 0.051(12) Uiso 1 1 d . . . H51Z H 0.065(2) 0.616(2) 0.4396(16) 0.045(12) Uiso 1 1 d . . . H28X H -0.224(2) 0.591(3) 0.2757(17) 0.056(13) Uiso 1 1 d . . . H44A H -0.353(2) 0.741(2) 0.0987(17) 0.050(12) Uiso 1 1 d . . . H92B H 0.0572(19) 0.441(2) 0.5805(15) 0.045(11) Uiso 1 1 d . . . H43A H -0.3279(19) 0.630(2) 0.0734(15) 0.039(10) Uiso 1 1 d . . . H61Y H 0.1495(18) 0.823(2) 0.1969(15) 0.035(10) Uiso 1 1 d . . . H51C H 0.222(2) 0.336(2) 0.0628(15) 0.040(11) Uiso 1 1 d . . . H42 H 0.7317(17) 0.454(2) 0.4106(14) 0.036(10) Uiso 1 1 d . . . H53C H 0.4411(16) 0.4225(19) 0.0686(13) 0.026(9) Uiso 1 1 d . . . H28A H 0.717(3) 0.433(3) 0.220(2) 0.076(17) Uiso 1 1 d . . . H63X H 0.0623(19) 0.555(2) 0.2119(14) 0.038(10) Uiso 1 1 d . . . H63C H 0.327(2) 0.229(2) 0.2524(16) 0.042(11) Uiso 1 1 d . . . H91B H 0.063(2) 0.326(3) 0.6127(18) 0.061(14) Uiso 1 1 d . . . H83B H 0.3337(18) 0.527(2) 0.8849(15) 0.037(10) Uiso 1 1 d . . . H61B H 0.460(2) 0.404(3) 0.3190(19) 0.059(14) Uiso 1 1 d . . . H33 H 0.8053(17) 0.038(2) 0.3124(13) 0.029(9) Uiso 1 1 d . . . H71B H 0.323(3) 0.086(3) 0.213(2) 0.084(17) Uiso 1 1 d . . . H90B H 0.169(2) 0.313(2) 0.6479(17) 0.047(11) Uiso 1 1 d . . . H82A H 0.4453(19) 0.561(2) 0.9802(16) 0.042(11) Uiso 1 1 d . . . H41A H -0.140(2) 0.654(2) 0.1272(16) 0.045(11) Uiso 1 1 d . . . H18A H 0.722(3) 0.204(4) 0.205(3) 0.11(3) Uiso 1 1 d . . . H43 H 0.824(2) 0.398(3) 0.4177(17) 0.056(14) Uiso 1 1 d . . . H80B H 0.3341(19) 0.653(2) 0.8548(16) 0.043(11) Uiso 1 1 d . . . H63Y H 0.005(2) 0.607(2) 0.2115(15) 0.040(11) Uiso 1 1 d . . . H72Y H 0.1016(16) 1.030(2) 0.3034(13) 0.027(9) Uiso 1 1 d . . . H24 H 0.5504(18) 0.641(2) 0.1439(14) 0.040(10) Uiso 1 1 d . . . H14 H 0.549(2) 0.025(3) 0.0398(18) 0.061(13) Uiso 1 1 d . . . H28B H 0.717(3) 0.385(3) 0.267(2) 0.076(17) Uiso 1 1 d . . . H28Y H -0.214(2) 0.577(3) 0.2217(18) 0.062(14) Uiso 1 1 d . . . H28Z H -0.219(2) 0.654(3) 0.2393(17) 0.059(13) Uiso 1 1 d . . . H82B H 0.445(2) 0.523(2) 0.9311(15) 0.047(12) Uiso 1 1 d . . . H81B H 0.432(2) 0.636(2) 0.8818(17) 0.054(12) Uiso 1 1 d . . . H18Y H -0.222(5) 0.856(6) 0.262(4) 0.24(5) Uiso 1 1 d . . . H18X H -0.219(3) 0.895(4) 0.299(3) 0.13(3) Uiso 1 1 d . . . H61C H 0.436(2) 0.480(2) 0.2813(15) 0.048(11) Uiso 1 1 d . . . H53Z H 0.2536(19) 0.757(2) 0.4266(15) 0.042(11) Uiso 1 1 d . . . H15 H 0.460(3) 0.058(3) 0.038(2) 0.09(2) Uiso 1 1 d . . . H63Z H 0.0348(19) 0.630(2) 0.1798(16) 0.041(11) Uiso 1 1 d . . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11

189

_atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Zr1 0.01209(12) 0.01691(13) 0.02093(13) -0.00018(8) 0.00512(9) -0.00039(8) Zr2 0.01219(12) 0.01647(12) 0.01969(13) 0.00135(8) 0.00528(9) 0.00019(8) N1 0.0140(10) 0.0239(11) 0.0231(11) -0.0042(8) 0.0050(8) 0.0000(8) N2 0.0157(10) 0.0177(10) 0.0240(11) -0.0003(8) 0.0055(8) -0.0010(8) N3 0.0180(10) 0.0260(12) 0.0287(12) 0.0026(9) 0.0070(9) -0.0010(9) N4 0.0190(10) 0.0187(10) 0.0273(11) 0.0018(8) 0.0100(9) 0.0017(8) N1A 0.0145(9) 0.0190(10) 0.0227(10) -0.0036(8) 0.0069(8) -0.0007(8) N2A 0.0169(10) 0.0147(9) 0.0241(11) 0.0008(8) 0.0077(8) 0.0008(8) N3A 0.0186(11) 0.0231(11) 0.0276(12) 0.0030(9) 0.0073(9) 0.0023(9) N4A 0.0183(10) 0.0200(10) 0.0246(11) 0.0029(8) 0.0091(8) 0.0006(8) O1 0.0179(9) 0.0162(8) 0.0354(11) -0.0003(7) 0.0069(8) -0.0020(7) O2 0.0326(13) 0.0398(14) 0.0555(16) 0.0030(11) 0.0224(11) 0.0009(10) O3 0.0361(13) 0.0386(13) 0.0510(15) -0.0025(11) 0.0270(11) -0.0011(10) O4 0.0493(17) 0.0368(14) 0.095(2) 0.0031(15) 0.0263(16) 0.0094(13) O1A 0.0169(8) 0.0173(8) 0.0272(10) 0.0024(7) 0.0053(7) -0.0006(7) C1 0.0151(11) 0.0174(11) 0.0228(12) -0.0014(9) 0.0067(9) 0.0016(9) C2 0.0183(12) 0.0241(13) 0.0233(13) -0.0004(10) 0.0095(10) 0.0014(10) C3 0.0227(13) 0.0229(12) 0.0224(12) 0.0011(10) 0.0094(10) 0.0015(10) C10 0.0135(11) 0.0181(11) 0.0215(12) -0.0002(9) 0.0056(9) 0.0003(9) C11 0.0176(11) 0.0188(11) 0.0247(12) -0.0001(9) 0.0096(9) 0.0008(9) C12 0.0219(12) 0.0250(13) 0.0235(13) -0.0045(10) 0.0078(10) 0.0025(10) C13 0.0338(17) 0.0392(18) 0.0320(16) -0.0124(13) 0.0119(13) 0.0062(14) C14 0.045(2) 0.055(2) 0.0381(19) -0.0264(18) 0.0084(16) 0.0091(18) C15 0.039(2) 0.058(2) 0.042(2) -0.0329(18) 0.0045(16) -0.0051(17) C16 0.0238(15) 0.0438(19) 0.0361(17) -0.0176(14) 0.0058(12) -0.0018(13) C17 0.0209(12) 0.0235(13) 0.0264(13) -0.0082(10) 0.0081(10) -0.0012(10) C18 0.0149(12) 0.0308(15) 0.0352(16) -0.0017(12) 0.0094(11) 0.0046(11) C20 0.0147(11) 0.0175(11) 0.0251(12) -0.0028(9) 0.0077(9) -0.0012(9) C21 0.0157(11) 0.0188(12) 0.0286(13) -0.0047(10) 0.0079(10) -0.0025(9) C22 0.0209(12) 0.0171(11) 0.0266(13) -0.0064(10) 0.0099(10) -0.0055(10) C23 0.0269(14) 0.0205(13) 0.0324(15) -0.0045(11) 0.0095(12) -0.0085(11) C24 0.0370(16) 0.0181(12) 0.0328(15) -0.0014(11) 0.0102(13) -0.0037(12) C25 0.0327(16) 0.0210(13) 0.0306(15) 0.0011(11) 0.0061(12) 0.0026(12) C26 0.0232(13) 0.0218(13) 0.0281(14) 0.0021(10) 0.0070(11) 0.0004(10) C27 0.0175(11) 0.0195(12) 0.0231(12) -0.0009(9) 0.0065(9) -0.0018(9) C28 0.0147(12) 0.0265(14) 0.0431(18) -0.0028(13) 0.0067(12) -0.0041(10) C30 0.0250(13) 0.0189(12) 0.0229(12) 0.0036(9) 0.0097(10) 0.0022(10) C31 0.0346(16) 0.0224(13) 0.0350(16) 0.0019(11) 0.0133(13) -0.0005(12) C32 0.0438(19) 0.0187(14) 0.0443(19) 0.0001(13) 0.0194(15) 0.0044(13) C33 0.0389(18) 0.0281(15) 0.0415(18) 0.0077(13) 0.0181(15) 0.0123(14) C34 0.0273(15) 0.0323(15) 0.0314(15) 0.0088(12) 0.0093(12) 0.0079(12)

190

C35 0.0256(13) 0.0236(13) 0.0222(12) 0.0038(10) 0.0069(10) 0.0032(11) C40 0.0278(14) 0.0224(13) 0.0184(12) 0.0003(9) 0.0075(10) 0.0004(10) C41 0.0401(18) 0.0279(15) 0.0242(14) -0.0029(11) 0.0071(13) 0.0050(13) C42 0.053(2) 0.0279(15) 0.0249(15) -0.0076(12) 0.0051(14) -0.0017(15) C43 0.043(2) 0.0350(17) 0.0279(16) -0.0049(13) -0.0016(14) -0.0139(15) C44 0.0272(15) 0.0328(16) 0.0265(14) 0.0006(12) 0.0005(11) -0.0030(13) C45 0.0274(14) 0.0233(13) 0.0207(12) 0.0024(10) 0.0057(10) 0.0007(11) C50 0.0179(12) 0.0305(15) 0.0344(16) 0.0055(12) 0.0073(11) 0.0024(11) C51 0.0184(14) 0.043(2) 0.0431(19) 0.0104(15) 0.0001(13) -0.0022(13) C52 0.0211(13) 0.0365(16) 0.0248(14) -0.0011(12) 0.0036(10) 0.0024(12) C53 0.0269(15) 0.0439(19) 0.0278(15) 0.0050(13) 0.0088(12) 0.0006(13) C60 0.0235(13) 0.0207(13) 0.0364(16) -0.0001(11) 0.0129(12) -0.0018(11) C61 0.044(2) 0.0297(17) 0.043(2) -0.0102(14) 0.0109(16) -0.0040(15) C62 0.0227(13) 0.0250(13) 0.0256(13) 0.0051(10) 0.0103(11) 0.0047(11) C63 0.0284(16) 0.0319(16) 0.0425(19) 0.0113(14) 0.0204(14) 0.0044(12) C70 0.0171(12) 0.0250(14) 0.0399(17) -0.0014(12) 0.0065(11) -0.0015(11) C71 0.0264(15) 0.0229(14) 0.053(2) 0.0041(13) 0.0109(14) -0.0072(12) C72 0.0348(16) 0.0169(12) 0.0428(18) -0.0032(12) 0.0140(14) -0.0054(11) C73 0.0249(14) 0.0164(12) 0.0381(16) 0.0035(11) 0.0095(12) 0.0019(10) C1A 0.0134(11) 0.0158(11) 0.0212(12) 0.0001(9) 0.0062(9) -0.0017(8) C2A 0.0187(12) 0.0216(12) 0.0214(12) 0.0003(10) 0.0076(9) -0.0016(10) C3A 0.0289(14) 0.0190(12) 0.0182(12) 0.0004(9) 0.0065(10) 0.0010(10) C10A 0.0155(11) 0.0159(11) 0.0210(12) -0.0002(9) 0.0061(9) -0.0013(9) C11A 0.0181(11) 0.0185(11) 0.0240(12) 0.0004(9) 0.0082(10) 0.0013(9) C12A 0.0218(12) 0.0173(11) 0.0233(12) 0.0000(9) 0.0102(10) 0.0015(9) C13A 0.0307(15) 0.0276(14) 0.0244(13) -0.0012(11) 0.0120(11) 0.0076(12) C14A 0.0481(19) 0.0279(15) 0.0230(14) -0.0072(11) 0.0154(13) 0.0027(13) C15A 0.0389(17) 0.0298(15) 0.0236(14) -0.0071(11) 0.0069(12) -0.0058(13) C16A 0.0245(14) 0.0263(13) 0.0249(13) -0.0041(11) 0.0081(11) -0.0045(11) C17A 0.0187(12) 0.0182(11) 0.0223(12) -0.0001(9) 0.0078(9) 0.0004(9) C18A 0.0171(12) 0.0297(15) 0.0324(15) -0.0026(12) 0.0080(11) 0.0036(11) C20A 0.0157(11) 0.0151(10) 0.0206(11) -0.0012(9) 0.0078(9) 0.0012(9) C21A 0.0185(11) 0.0175(11) 0.0221(12) -0.0033(9) 0.0077(9) -0.0012(9) C22A 0.0228(12) 0.0176(11) 0.0218(12) -0.0034(9) 0.0109(10) 0.0004(9) C23A 0.0249(13) 0.0164(11) 0.0296(14) -0.0014(10) 0.0114(11) -0.0045(10) C24A 0.0380(16) 0.0155(12) 0.0316(15) 0.0010(11) 0.0126(13) -0.0006(11) C25A 0.0320(15) 0.0209(13) 0.0283(14) 0.0024(11) 0.0088(12) 0.0046(11) C26A 0.0202(12) 0.0237(13) 0.0272(13) 0.0012(10) 0.0066(10) 0.0011(10) C27A 0.0204(12) 0.0164(11) 0.0205(12) -0.0001(9) 0.0088(9) 0.0011(9) C28A 0.0174(12) 0.0209(13) 0.0389(17) -0.0031(12) 0.0068(11) -0.0049(10) C30A 0.0231(12) 0.0198(12) 0.0212(12) 0.0043(9) 0.0067(10) 0.0009(10) C31A 0.0296(15) 0.0188(12) 0.0341(15) 0.0006(11) 0.0139(12) -0.0033(11) C32A 0.0464(19) 0.0173(13) 0.0415(18) -0.0025(12) 0.0167(15) 0.0031(13) C33A 0.0378(17) 0.0267(15) 0.0434(18) 0.0076(13) 0.0188(14) 0.0128(13) C34A 0.0239(14) 0.0302(15) 0.0348(16) 0.0057(12) 0.0076(12) 0.0072(12) C35A 0.0227(13) 0.0225(12) 0.0227(13) 0.0027(10) 0.0059(10) 0.0007(10)

191

C40A 0.0232(12) 0.0177(11) 0.0207(12) 0.0015(9) 0.0084(10) 0.0007(10) C41A 0.0418(18) 0.0241(14) 0.0221(13) -0.0030(11) 0.0085(12) 0.0017(13) C42A 0.064(2) 0.0228(15) 0.0315(16) -0.0049(12) 0.0128(16) -0.0027(15) C43A 0.050(2) 0.0341(17) 0.0289(16) -0.0086(13) -0.0014(14) -0.0158(16) C44A 0.0306(16) 0.0395(17) 0.0278(15) -0.0011(13) 0.0030(12) -0.0076(14) C45A 0.0286(14) 0.0219(12) 0.0205(12) 0.0009(10) 0.0049(10) -0.0016(11) C50A 0.0238(14) 0.0336(16) 0.0239(13) 0.0006(11) 0.0050(11) 0.0043(12) C51A 0.0345(18) 0.052(2) 0.0258(16) 0.0109(15) 0.0107(13) 0.0063(16) C52A 0.0199(13) 0.0351(16) 0.0339(16) 0.0055(13) 0.0074(11) 0.0047(12) C53A 0.0193(14) 0.049(2) 0.042(2) 0.0057(16) 0.0015(13) 0.0010(14) C60A 0.0182(12) 0.0215(12) 0.0254(13) 0.0051(10) 0.0088(10) 0.0028(10) C61A 0.0254(15) 0.0274(15) 0.0399(18) 0.0105(13) 0.0181(13) 0.0046(12) C62A 0.0280(14) 0.0190(12) 0.0327(15) 0.0026(11) 0.0155(12) 0.0053(11) C63A 0.047(2) 0.0306(17) 0.044(2) -0.0098(15) 0.0156(16) -0.0026(15) C70A 0.0199(13) 0.0263(14) 0.0330(15) -0.0026(11) 0.0070(11) -0.0063(11) C71A 0.0231(15) 0.0270(15) 0.052(2) -0.0012(15) 0.0118(14) -0.0073(12) C72A 0.0316(15) 0.0232(14) 0.0305(15) -0.0029(11) 0.0114(12) -0.0035(11) C73A 0.0236(13) 0.0206(12) 0.0319(15) 0.0045(11) 0.0071(11) 0.0014(10) C80 0.0322(17) 0.045(2) 0.0420(19) 0.0031(15) 0.0171(14) 0.0027(15) C81 0.0295(16) 0.049(2) 0.0385(18) -0.0040(16) 0.0142(14) -0.0046(15) C82 0.0342(19) 0.045(2) 0.055(2) 0.0067(18) 0.0097(17) 0.0057(16) C83 0.0391(19) 0.0384(19) 0.052(2) 0.0013(17) 0.0170(17) -0.0043(15) C90 0.0398(19) 0.0432(19) 0.0342(17) 0.0005(14) 0.0167(14) 0.0020(15) C91 0.0344(17) 0.046(2) 0.0340(17) -0.0103(14) 0.0196(14) -0.0047(14) C92 0.0383(19) 0.045(2) 0.0404(19) -0.0033(16) 0.0103(15) 0.0056(16) C93 0.045(2) 0.0325(17) 0.051(2) -0.0056(15) 0.0262(17) -0.0013(15) C101 0.085(3) 0.040(2) 0.053(2) -0.0039(18) 0.023(2) 0.002(2) C102 0.057(3) 0.062(3) 0.062(3) -0.017(2) 0.006(2) 0.019(2) C103 0.050(3) 0.059(3) 0.082(3) -0.009(2) 0.025(2) 0.010(2) C110 0.060(3) 0.068(3) 0.071(3) 0.033(3) 0.007(2) -0.009(2) C111 0.045(2) 0.051(2) 0.041(2) 0.0043(17) 0.0178(16) 0.0051(17) C112 0.060(3) 0.059(3) 0.135(5) 0.041(3) 0.019(3) 0.005(3) C113 0.068(3) 0.061(3) 0.087(4) 0.031(3) 0.013(3) -0.016(2)

192

_geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Zr1 N3 2.012(2) . ? Zr1 N4 2.038(2) . ? Zr1 N2 2.194(2) . ? Zr1 N1 2.202(2) . ? Zr1 O1 2.2843(19) . ? Zr2 N3A 2.015(2) . ? Zr2 N4A 2.030(2) . ? Zr2 N2A 2.191(2) . ? Zr2 N1A 2.213(2) . ? Zr2 O1A 2.2911(19) . ? N1 C10 1.392(3) . ? N1 C17 1.393(3) . ? N2 C27 1.389(3) . ? N2 C20 1.397(3) . ? N3 C50 1.469(4) . ? N3 C52 1.474(4) . ? N4 C62 1.455(4) . ? N4 C60 1.463(4) . ? N1A C10A 1.388(3) . ? N1A C17A 1.390(3) . ? N2A C27A 1.395(3) . ? N2A C20A 1.407(3) . ? N3A C52A 1.470(4) . ? N3A C50A 1.471(4) . ? N4A C60A 1.460(3) . ? N4A C62A 1.472(4) . ? O1 C70 1.467(3) . ? O1 C73 1.476(3) . ? O2 C83 1.429(5) . ? O2 C80 1.432(4) . ? O3 C93 1.419(4) . ? O3 C90 1.432(4) . ? O4 C103 1.404(5) . ? O4 C200 1.409(12) . ? O4 C100 1.498(12) . ? O5 C110 1.348(9) . ? O5 C113 1.429(9) . ? O5A C113 1.439(7) . ? O5A C110 1.494(8) . ? O6 C123 1.363(9) . ? O6 C120 1.507(11) . ? O1A C70A 1.473(3) . ?

193

O1A C73A 1.476(3) . ? C1 C10 1.506(4) . ? C1 C20 1.512(4) . ? C1 C2 1.566(4) . ? C2 C3 1.543(4) . ? C3 C40 1.507(4) . ? C3 C30 1.523(4) . ? C10 C11 1.376(3) . ? C11 C12 1.433(4) . ? C11 C18 1.495(4) . ? C12 C13 1.406(4) . ? C12 C17 1.410(4) . ? C13 C14 1.381(5) . ? C14 C15 1.387(5) . ? C15 C16 1.379(5) . ? C16 C17 1.400(4) . ? C20 C21 1.382(4) . ? C21 C22 1.435(4) . ? C21 C28 1.500(4) . ? C22 C23 1.399(4) . ? C22 C27 1.419(4) . ? C23 C24 1.385(4) . ? C24 C25 1.392(4) . ? C25 C26 1.392(4) . ? C26 C27 1.406(4) . ? C30 C31 1.388(4) . ? C30 C35 1.402(4) . ? C31 C32 1.402(5) . ? C32 C33 1.385(5) . ? C33 C34 1.389(5) . ? C34 C35 1.388(4) . ? C35 C45 1.475(4) . ? C40 C41 1.396(4) . ? C40 C45 1.401(4) . ? C41 C42 1.397(5) . ? C42 C43 1.369(6) . ? C43 C44 1.396(5) . ? C44 C45 1.392(4) . ? C50 C51 1.527(4) . ? C52 C53 1.526(5) . ? C60 C61 1.531(5) . ? C62 C63 1.517(4) . ? C70 C71 1.524(4) . ? C71 C72 1.526(5) . ? C72 C73 1.516(4) . ? C1A C20A 1.509(3) . ?

194

C1A C10A 1.510(3) . ? C1A C2A 1.551(4) . ? C2A C40A 1.537(4) . ? C3A C41A 1.396(4) . ? C3A C45A 1.400(4) . ? C3A C40A 1.509(4) . ? C10A C11A 1.372(4) . ? C11A C12A 1.431(4) . ? C11A C18A 1.495(4) . ? C12A C13A 1.402(4) . ? C12A C17A 1.422(4) . ? C13A C14A 1.388(4) . ? C14A C15A 1.380(5) . ? C15A C16A 1.398(4) . ? C16A C17A 1.392(4) . ? C20A C21A 1.373(4) . ? C21A C22A 1.433(4) . ? C21A C28A 1.492(4) . ? C22A C23A 1.408(4) . ? C22A C27A 1.421(4) . ? C23A C24A 1.388(4) . ? C24A C25A 1.397(4) . ? C25A C26A 1.390(4) . ? C26A C27A 1.403(4) . ? C30A C31A 1.387(4) . ? C30A C35A 1.398(4) . ? C30A C40A 1.518(4) . ? C31A C32A 1.399(4) . ? C32A C33A 1.383(5) . ? C33A C34A 1.389(5) . ? C34A C35A 1.390(4) . ? C35A C45A 1.469(4) . ? C41A C42A 1.384(5) . ? C42A C43A 1.387(6) . ? C43A C44A 1.392(5) . ? C44A C45A 1.396(4) . ? C50A C51A 1.527(5) . ? C52A C53A 1.525(5) . ? C60A C61A 1.519(4) . ? C62A C63A 1.514(5) . ? C70A C71A 1.508(5) . ? C71A C72A 1.518(5) . ? C72A C73A 1.507(4) . ? C80 C81 1.524(5) . ? C81 C82 1.528(6) . ? C82 C83 1.514(5) . ?

195

C90 C91 1.517(5) . ? C91 C92 1.527(6) . ? C92 C93 1.510(5) . ? C100 C101 1.531(12) . ? C200 C101 1.436(13) . ? C101 C102 1.531(7) . ? C102 C103 1.538(7) . ? C110 C111 1.496(6) . ? C111 C112 1.525(7) . ? C112 C113 1.518(7) . ? C120 C121 1.510(12) . ? C121 C122 1.420(13) . ? O7 C130 1.530(9) . ? O7 C133 1.595(9) . ? C133 C132 1.593(9) . ? C131 C130 1.284(9) . ? C131 C132 1.411(8) . ? C123 C122 1.493(13) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag N3 Zr1 N4 109.45(10) . . ? N3 Zr1 N2 103.28(9) . . ? N4 Zr1 N2 96.84(9) . . ? N3 Zr1 N1 116.10(9) . . ? N4 Zr1 N1 133.03(9) . . ? N2 Zr1 N1 83.75(8) . . ? N3 Zr1 O1 98.41(9) . . ? N4 Zr1 O1 85.01(8) . . ? N2 Zr1 O1 156.16(8) . . ? N1 Zr1 O1 77.88(8) . . ? N3A Zr2 N4A 109.22(9) . . ? N3A Zr2 N2A 102.97(9) . . ? N4A Zr2 N2A 96.78(9) . . ? N3A Zr2 N1A 117.26(9) . . ? N4A Zr2 N1A 132.14(9) . . ? N2A Zr2 N1A 83.85(8) . . ? N3A Zr2 O1A 96.51(8) . . ? N4A Zr2 O1A 86.15(8) . . ? N2A Zr2 O1A 158.04(7) . . ?

196

N1A Zr2 O1A 78.22(7) . . ? C10 N1 C17 105.6(2) . . ? C10 N1 Zr1 123.07(17) . . ? C17 N1 Zr1 130.50(17) . . ? C27 N2 C20 105.0(2) . . ? C27 N2 Zr1 132.49(17) . . ? C20 N2 Zr1 122.04(17) . . ? C50 N3 C52 115.2(2) . . ? C50 N3 Zr1 131.5(2) . . ? C52 N3 Zr1 113.23(17) . . ? C62 N4 C60 115.1(2) . . ? C62 N4 Zr1 131.47(18) . . ? C60 N4 Zr1 112.80(18) . . ? C10A N1A C17A 105.8(2) . . ? C10A N1A Zr2 122.55(16) . . ? C17A N1A Zr2 130.81(17) . . ? C27A N2A C20A 104.7(2) . . ? C27A N2A Zr2 132.63(17) . . ? C20A N2A Zr2 122.08(16) . . ? C52A N3A C50A 115.6(2) . . ? C52A N3A Zr2 131.0(2) . . ? C50A N3A Zr2 113.34(17) . . ? C60A N4A C62A 114.2(2) . . ? C60A N4A Zr2 130.89(18) . . ? C62A N4A Zr2 114.54(17) . . ? C70 O1 C73 109.6(2) . . ? C70 O1 Zr1 118.60(16) . . ? C73 O1 Zr1 131.60(16) . . ? C83 O2 C80 104.0(3) . . ? C93 O3 C90 104.0(3) . . ? C103 O4 C200 110.2(6) . . ? C103 O4 C100 108.8(5) . . ? C200 O4 C100 15.4(6) . . ? C110 O5 C113 112.0(6) . . ? C113 O5A C110 103.4(5) . . ? C123 O6 C120 107.8(7) . . ? C70A O1A C73A 109.3(2) . . ? C70A O1A Zr2 120.72(16) . . ? C73A O1A Zr2 129.89(16) . . ? C10 C1 C20 109.7(2) . . ? C10 C1 C2 112.0(2) . . ? C20 C1 C2 111.8(2) . . ? C3 C2 C1 113.4(2) . . ? C40 C3 C30 102.0(2) . . ? C40 C3 C2 115.0(2) . . ? C30 C3 C2 114.6(2) . . ?

197

C11 C10 N1 112.0(2) . . ? C11 C10 C1 128.9(2) . . ? N1 C10 C1 119.1(2) . . ? C10 C11 C12 105.8(2) . . ? C10 C11 C18 128.3(3) . . ? C12 C11 C18 125.9(2) . . ? C13 C12 C17 119.9(3) . . ? C13 C12 C11 133.2(3) . . ? C17 C12 C11 106.9(2) . . ? C14 C13 C12 118.4(3) . . ? C13 C14 C15 121.2(3) . . ? C16 C15 C14 121.8(3) . . ? C15 C16 C17 117.9(3) . . ? N1 C17 C16 129.5(3) . . ? N1 C17 C12 109.6(2) . . ? C16 C17 C12 120.9(3) . . ? C21 C20 N2 112.5(2) . . ? C21 C20 C1 126.9(2) . . ? N2 C20 C1 120.5(2) . . ? C20 C21 C22 105.6(2) . . ? C20 C21 C28 128.0(3) . . ? C22 C21 C28 126.3(2) . . ? C23 C22 C27 119.9(3) . . ? C23 C22 C21 133.5(3) . . ? C27 C22 C21 106.5(2) . . ? C24 C23 C22 119.3(3) . . ? C23 C24 C25 120.5(3) . . ? C26 C25 C24 121.8(3) . . ? C25 C26 C27 117.9(3) . . ? N2 C27 C26 129.2(2) . . ? N2 C27 C22 110.3(2) . . ? C26 C27 C22 120.4(2) . . ? C31 C30 C35 120.7(3) . . ? C31 C30 C3 128.9(3) . . ? C35 C30 C3 110.4(2) . . ? C30 C31 C32 118.1(3) . . ? C33 C32 C31 121.0(3) . . ? C32 C33 C34 120.9(3) . . ? C35 C34 C33 118.6(3) . . ? C34 C35 C30 120.7(3) . . ? C34 C35 C45 130.9(3) . . ? C30 C35 C45 108.4(2) . . ? C41 C40 C45 119.8(3) . . ? C41 C40 C3 129.1(3) . . ? C45 C40 C3 111.0(2) . . ? C40 C41 C42 118.9(3) . . ?

198

C43 C42 C41 120.6(3) . . ? C42 C43 C44 121.8(3) . . ? C45 C44 C43 117.8(3) . . ? C44 C45 C40 121.1(3) . . ? C44 C45 C35 130.7(3) . . ? C40 C45 C35 108.1(2) . . ? N3 C50 C51 114.8(3) . . ? N3 C52 C53 114.2(3) . . ? N4 C60 C61 114.6(3) . . ? N4 C62 C63 114.1(2) . . ? O1 C70 C71 104.6(2) . . ? C70 C71 C72 102.4(3) . . ? C73 C72 C71 101.8(2) . . ? O1 C73 C72 104.3(2) . . ? C20A C1A C10A 109.9(2) . . ? C20A C1A C2A 113.2(2) . . ? C10A C1A C2A 112.3(2) . . ? C40A C2A C1A 113.7(2) . . ? C41A C3A C45A 119.9(3) . . ? C41A C3A C40A 129.7(3) . . ? C45A C3A C40A 110.4(2) . . ? C11A C10A N1A 112.4(2) . . ? C11A C10A C1A 128.9(2) . . ? N1A C10A C1A 118.6(2) . . ? C10A C11A C12A 105.7(2) . . ? C10A C11A C18A 128.4(2) . . ? C12A C11A C18A 125.9(2) . . ? C13A C12A C17A 119.7(3) . . ? C13A C12A C11A 133.4(3) . . ? C17A C12A C11A 106.8(2) . . ? C14A C13A C12A 118.6(3) . . ? C15A C14A C13A 121.4(3) . . ? C14A C15A C16A 121.3(3) . . ? C17A C16A C15A 118.2(3) . . ? N1A C17A C16A 130.0(2) . . ? N1A C17A C12A 109.2(2) . . ? C16A C17A C12A 120.8(2) . . ? C21A C20A N2A 112.6(2) . . ? C21A C20A C1A 127.8(2) . . ? N2A C20A C1A 119.4(2) . . ? C20A C21A C22A 105.9(2) . . ? C20A C21A C28A 127.7(2) . . ? C22A C21A C28A 126.4(2) . . ? C23A C22A C27A 120.0(2) . . ? C23A C22A C21A 133.2(3) . . ? C27A C22A C21A 106.7(2) . . ?

199

C24A C23A C22A 118.1(3) . . ? C23A C24A C25A 121.7(3) . . ? C26A C25A C24A 121.2(3) . . ? C25A C26A C27A 118.0(3) . . ? N2A C27A C26A 129.1(2) . . ? N2A C27A C22A 110.1(2) . . ? C26A C27A C22A 120.9(2) . . ? C31A C30A C35A 120.7(3) . . ? C31A C30A C40A 129.0(3) . . ? C35A C30A C40A 110.3(2) . . ? C30A C31A C32A 118.3(3) . . ? C33A C32A C31A 120.9(3) . . ? C32A C33A C34A 120.8(3) . . ? C33A C34A C35A 118.7(3) . . ? C34A C35A C30A 120.6(3) . . ? C34A C35A C45A 131.0(3) . . ? C30A C35A C45A 108.4(2) . . ? C3A C40A C30A 102.2(2) . . ? C3A C40A C2A 113.7(2) . . ? C30A C40A C2A 115.5(2) . . ? C42A C41A C3A 118.9(3) . . ? C43A C42A C41A 120.9(3) . . ? C42A C43A C44A 121.2(3) . . ? C43A C44A C45A 117.8(3) . . ? C44A C45A C3A 121.3(3) . . ? C44A C45A C35A 130.2(3) . . ? C3A C45A C35A 108.6(2) . . ? N3A C50A C51A 114.7(3) . . ? N3A C52A C53A 114.5(3) . . ? N4A C60A C61A 113.4(2) . . ? N4A C62A C63A 115.3(3) . . ? O1A C70A C71A 104.6(2) . . ? C70A C71A C72A 103.0(3) . . ? C73A C72A C71A 102.1(3) . . ? O1A C73A C72A 104.3(2) . . ? O2 C80 C81 107.0(3) . . ? C80 C81 C82 104.3(3) . . ? C83 C82 C81 102.6(3) . . ? O2 C83 C82 105.7(3) . . ? O3 C90 C91 106.5(3) . . ? C90 C91 C92 104.4(3) . . ? C93 C92 C91 102.8(3) . . ? O3 C93 C92 106.1(3) . . ? O4 C100 C101 100.2(7) . . ? O4 C200 C101 109.6(8) . . ? C200 C101 C102 104.4(6) . . ?

200

C200 C101 C100 15.0(6) . . ? C102 C101 C100 99.9(5) . . ? C101 C102 C103 102.1(4) . . ? O4 C103 C102 106.8(4) . . ? O5 C110 O5A 26.2(3) . . ? O5 C110 C111 107.4(5) . . ? O5A C110 C111 110.0(4) . . ? C110 C111 C112 102.7(4) . . ? C113 C112 C111 104.1(4) . . ? O5 C113 O5A 26.6(3) . . ? O5 C113 C112 105.6(5) . . ? O5A C113 C112 104.8(5) . . ? C121 C120 O6 103.4(8) . . ? C122 C121 C120 106.0(9) . . ? C130 O7 C133 99.4(5) . . ? C132 C133 O7 98.3(5) . . ? C130 C131 C132 100.8(6) . . ? C131 C132 C133 104.7(6) . . ? O6 C123 C122 104.1(8) . . ? C131 C130 O7 109.1(7) . . ? C121 C122 C123 106.1(9) . . ?

_diffrn_measured_fraction_theta_max 0.921 _diffrn_reflns_theta_full 31.74 _diffrn_measured_fraction_theta_full 0.921 _refine_diff_density_max 2.522 _refine_diff_density_min -1.041 _refine_diff_density_rms 0.112

201

CIF File for (IDI)Zr(NEt2)

_audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C36.50 H37 N3 Zr' _chemical_formula_sum 'C36.50 H37 N3 Zr' _chemical_formula_weight 608.91 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source 'C' 'C' 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'H' 'H' 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'N' 'N' 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'Zr' 'Zr' -2.9673 0.5597 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting tetragonal _symmetry_space_group_name_H-M I4(1)/a loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y, z+1/2' '-y+3/4, x+1/4, z+1/4' 'y+3/4, -x+3/4, z+3/4' 'x+1/2, y+1/2, z+1/2' '-x+1, -y+1/2, z+1' '-y+5/4, x+3/4, z+3/4' 'y+5/4, -x+5/4, z+5/4' '-x, -y, -z' 'x-1/2, y, -z-1/2' 'y-3/4, -x-1/4, -z-1/4' '-y-3/4, x-3/4, -z-3/4' '-x+1/2, -y+1/2, -z+1/2'

202

'x, y+1/2, -z' 'y-1/4, -x+1/4, -z+1/4' '-y-1/4, x-1/4, -z-1/4'

_cell_length_a 22.1251(18) _cell_length_b 22.1251(18) _cell_length_c 24.479(3) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 11982.7(19) _cell_formula_units_Z 16 _cell_measurement_temperature 150(2) _cell_measurement_reflns_used 370 _cell_measurement_theta_min 2.0 _cell_measurement_theta_max 30.0

_exptl_crystal_description 'tetragonal bipyramid' _exptl_crystal_colour 'yellow' _exptl_crystal_size_max .30 _exptl_crystal_size_mid .30 _exptl_crystal_size_min .25 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.350 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 5072 _exptl_absorpt_coefficient_mu 0.397 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.848 _exptl_absorpt_correction_T_max 1.000 _exptl_absorpt_process_details ?

_exptl_special_details ; ? ;

_diffrn_ambient_temperature 150(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Bruker platform with 6k CCD' _diffrn_measurement_method 'omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ?

203

_diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 51513 _diffrn_reflns_av_R_equivalents 0.0377 _diffrn_reflns_av_sigmaI/netI 0.0204 _diffrn_reflns_limit_h_min -28 _diffrn_reflns_limit_h_max 31 _diffrn_reflns_limit_k_min -31 _diffrn_reflns_limit_k_max 30 _diffrn_reflns_limit_l_min -34 _diffrn_reflns_limit_l_max 29 _diffrn_reflns_theta_min 1.24 _diffrn_reflns_theta_max 30.14 _reflns_number_total 8825 _reflns_number_gt 7717 _reflns_threshold_expression >2sigma(I)

_refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0542P)^2^+15.9443P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens difmap _refine_ls_hydrogen_treatment refall

204

_refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 8825 _refine_ls_number_parameters 529 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0515 _refine_ls_R_factor_gt 0.0432 _refine_ls_wR_factor_ref 0.1151 _refine_ls_wR_factor_gt 0.1105 _refine_ls_goodness_of_fit_ref 1.150 _refine_ls_restrained_S_all 1.150 _refine_ls_shift/su_max 0.003 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Zr1 Zr 0.322732(8) 0.965822(8) 0.123943(7) 0.02047(6) Uani 1 1 d . . . N1 N 0.24526(8) 1.01528(7) 0.10083(7) 0.0264(3) Uani 1 1 d . . . N2 N 0.31495(7) 0.90790(7) 0.05328(6) 0.0218(3) Uani 1 1 d . . . N3 N 0.39403(8) 1.02015(8) 0.13625(7) 0.0274(3) Uani 1 1 d . . . C1 C 0.20278(8) 0.91287(9) 0.07427(8) 0.0255(4) Uani 1 1 d . . . C2 C 0.20203(9) 0.88002(10) 0.13130(9) 0.0278(4) Uani 1 1 d . . . C3 C 0.25363(9) 0.89611(9) 0.16890(8) 0.0256(4) Uani 1 1 d . . . C4 C 0.25533(10) 0.94799(9) 0.20325(8) 0.0288(4) Uani 1 1 d . . . C5 C 0.31338(10) 0.95499(10) 0.22529(8) 0.0302(4) Uani 1 1 d . . . C6 C 0.43580(12) 1.04243(11) 0.17797(10) 0.0362(5) Uani 1 1 d . . . C7 C 0.4286(2) 1.10888(17) 0.18992(18) 0.0730(11) Uani 1 1 d . . . C8 C 0.39973(9) 1.04820(9) 0.08220(8) 0.0270(4) Uani 1 1 d . . . C9 C 0.46035(10) 1.04007(12) 0.05455(10) 0.0362(5) Uani 1 1 d . . . C10 C 0.19735(9) 0.98093(9) 0.07962(8) 0.0264(4) Uani 1 1 d . . . C11 C 0.14824(10) 1.01644(10) 0.06793(9) 0.0331(4) Uani 1 1 d . . . C12 C 0.16455(10) 1.07671(10) 0.08379(10) 0.0351(5) Uani 1 1 d . . . C13 C 0.13358(13) 1.13253(12) 0.08376(13) 0.0477(6) Uani 1 1 d . . . C14 C 0.16298(15) 1.18281(12) 0.10417(15) 0.0566(8) Uani 1 1 d . . .

205

C15 C 0.22171(16) 1.17929(12) 0.12398(13) 0.0506(7) Uani 1 1 d . . . C16 C 0.25336(13) 1.12517(11) 0.12473(11) 0.0397(5) Uani 1 1 d . . . C17 C 0.22415(10) 1.07415(9) 0.10427(9) 0.0302(4) Uani 1 1 d . . . C18 C 0.08916(12) 0.99778(15) 0.04332(15) 0.0515(7) Uani 1 1 d . . . C20 C 0.25524(8) 0.89090(8) 0.04037(8) 0.0228(3) Uani 1 1 d . . . C21 C 0.25353(9) 0.85008(9) -0.00178(8) 0.0260(4) Uani 1 1 d . . . C22 C 0.31517(9) 0.83830(8) -0.01627(8) 0.0245(4) Uani 1 1 d . . . C23 C 0.34249(10) 0.79942(9) -0.05412(9) 0.0302(4) Uani 1 1 d . . . C24 C 0.40511(11) 0.79709(10) -0.05645(9) 0.0332(4) Uani 1 1 d . . . C25 C 0.44046(10) 0.83306(10) -0.02202(9) 0.0323(4) Uani 1 1 d . . . C26 C 0.41450(9) 0.87216(9) 0.01554(8) 0.0269(4) Uani 1 1 d . . . C27 C 0.35139(8) 0.87463(8) 0.01840(7) 0.0218(3) Uani 1 1 d . . . C28 C 0.19948(12) 0.82255(13) -0.02899(11) 0.0397(5) Uani 1 1 d . . . C30 C 0.31187(9) 0.86784(8) 0.17304(8) 0.0248(4) Uani 1 1 d . . . C31 C 0.33761(10) 0.81570(9) 0.14791(9) 0.0292(4) Uani 1 1 d . . . C32 C 0.39564(11) 0.80052(10) 0.16033(10) 0.0356(5) Uani 1 1 d . . . C33 C 0.43148(11) 0.83565(12) 0.19679(10) 0.0390(5) Uani 1 1 d . . . C34 C 0.40953(10) 0.88705(11) 0.21991(9) 0.0350(5) Uani 1 1 d . . . C35 C 0.34901(9) 0.90438(9) 0.20832(8) 0.0276(4) Uani 1 1 d . . . H1 H 0.1665(11) 0.9001(10) 0.0542(10) 0.025(6) Uiso 1 1 d . . . H2A H 0.1639(12) 0.8898(11) 0.1465(11) 0.030(6) Uiso 1 1 d . . . H2B H 0.2031(11) 0.8361(11) 0.1232(9) 0.025(6) Uiso 1 1 d . . . H4 H 0.2216(12) 0.9756(12) 0.2082(11) 0.034(7) Uiso 1 1 d . . . H5 H 0.3265(12) 0.9871(12) 0.2489(12) 0.038(7) Uiso 1 1 d . . . H6A H 0.4294(13) 1.0200(14) 0.2105(13) 0.048(8) Uiso 1 1 d . . . H6B H 0.4753(13) 1.0346(13) 0.1686(12) 0.037(7) Uiso 1 1 d . . . H7A H 0.4576(16) 1.1202(17) 0.2159(16) 0.068(11) Uiso 1 1 d . . . H7B H 0.435(2) 1.135(2) 0.156(2) 0.103(15) Uiso 1 1 d . . . H7C H 0.386(2) 1.117(2) 0.198(2) 0.107(17) Uiso 1 1 d . . . H8A H 0.3884(12) 1.0894(12) 0.0821(11) 0.036(7) Uiso 1 1 d . . . H8B H 0.3675(12) 1.0308(12) 0.0585(11) 0.033(6) Uiso 1 1 d . . . H9A H 0.4919(13) 1.0621(12) 0.0739(12) 0.039(7) Uiso 1 1 d . . . H9B H 0.4590(14) 1.0561(13) 0.0188(14) 0.049(8) Uiso 1 1 d . . . H9C H 0.4690(14) 0.9986(15) 0.0523(13) 0.053(9) Uiso 1 1 d . . . H13 H 0.0927(16) 1.1347(15) 0.0698(15) 0.063(10) Uiso 1 1 d . . . H14 H 0.1429(18) 1.2210(18) 0.1050(17) 0.077(11) Uiso 1 1 d . . . H15 H 0.2419(15) 1.2090(16) 0.1378(14) 0.053(9) Uiso 1 1 d . . . H16 H 0.2908(14) 1.1233(13) 0.1374(13) 0.042(8) Uiso 1 1 d . . . H23 H 0.3180(11) 0.7766(11) -0.0768(11) 0.028(6) Uiso 1 1 d . . . H24 H 0.4241(11) 0.7737(11) -0.0827(11) 0.030(6) Uiso 1 1 d . . . H25 H 0.4832(13) 0.8316(12) -0.0259(12) 0.043(8) Uiso 1 1 d . . . H26 H 0.4378(11) 0.8948(11) 0.0403(11) 0.029(6) Uiso 1 1 d . . . H28A H 0.1636(19) 0.8282(18) -0.0082(17) 0.083(12) Uiso 1 1 d . . . H28B H 0.2048(17) 0.7791(18) -0.0324(16) 0.077(11) Uiso 1 1 d . . . H28C H 0.1971(18) 0.8314(19) -0.0645(18) 0.084(13) Uiso 1 1 d . . . H31 H 0.3161(12) 0.7950(12) 0.1237(10) 0.028(6) Uiso 1 1 d . . .

206

H32 H 0.4133(12) 0.7674(12) 0.1448(11) 0.033(7) Uiso 1 1 d . . . H33 H 0.4736(14) 0.8225(13) 0.2048(13) 0.047(8) Uiso 1 1 d . . . H34 H 0.4313(13) 0.9111(13) 0.2436(13) 0.045(8) Uiso 1 1 d . . . H18C H 0.063(2) 1.031(2) 0.0441(18) 0.087(13) Uiso 1 1 d . . . H18B H 0.070(2) 0.969(2) 0.062(2) 0.108(16) Uiso 1 1 d . . . H18A H 0.089(3) 1.006(3) 0.002(3) 0.14(2) Uiso 1 1 d . . . C60 C 0.0034(3) 1.2653(2) 0.0415(2) 0.0439(14) Uani 0.50 1 d P . . C61 C -0.0169(3) 1.2067(3) 0.0565(3) 0.0485(13) Uani 0.50 1 d P . . C62 C -0.0316(2) 1.1651(3) 0.0160(3) 0.0458(11) Uani 0.50 1 d P . . C63 C -0.0279(3) 1.1806(3) -0.0376(3) 0.0433(13) Uani 0.50 1 d P . . C64 C -0.0082(4) 1.2391(3) -0.0529(2) 0.0461(15) Uani 0.50 1 d P . . C65 C 0.0072(2) 1.2816(2) -0.0138(2) 0.0417(11) Uani 0.50 1 d P . . C66 C 0.0268(4) 1.3452(3) -0.0303(5) 0.064(2) Uani 0.50 1 d P . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Zr1 0.02298(10) 0.02182(9) 0.01661(10) 0.00095(6) 0.00251(6) -0.00252(6) N1 0.0284(8) 0.0251(8) 0.0257(8) 0.0004(6) 0.0032(6) 0.0012(6) N2 0.0223(7) 0.0239(7) 0.0193(7) 0.0014(6) 0.0005(5) -0.0028(5) N3 0.0324(8) 0.0293(8) 0.0204(8) 0.0024(6) -0.0017(6) -0.0077(7) C1 0.0211(8) 0.0275(9) 0.0278(9) 0.0012(7) 0.0011(7) -0.0021(7) C2 0.0247(9) 0.0301(10) 0.0286(10) 0.0036(7) 0.0065(7) -0.0050(7) C3 0.0271(9) 0.0286(9) 0.0210(8) 0.0041(7) 0.0071(7) -0.0039(7) C4 0.0347(10) 0.0307(10) 0.0211(9) 0.0026(7) 0.0114(7) 0.0001(8) C5 0.0418(11) 0.0318(10) 0.0170(8) -0.0003(7) 0.0059(8) -0.0041(8) C6 0.0420(12) 0.0407(12) 0.0259(10) 0.0018(9) -0.0079(9) -0.0150(10) C7 0.107(3) 0.0519(18) 0.060(2) -0.0188(16) -0.035(2) -0.0095(19) C8 0.0281(9) 0.0288(9) 0.0240(9) 0.0053(7) -0.0024(7) -0.0058(7) C9 0.0293(10) 0.0461(13) 0.0330(12) 0.0096(10) 0.0013(8) -0.0071(9) C10 0.0251(9) 0.0294(9) 0.0246(9) 0.0034(7) 0.0044(7) 0.0007(7) C11 0.0279(10) 0.0373(11) 0.0340(11) 0.0090(9) 0.0049(8) 0.0051(8) C12 0.0348(11) 0.0350(11) 0.0357(11) 0.0096(9) 0.0114(9) 0.0089(8) C13 0.0450(14) 0.0406(13) 0.0575(17) 0.0160(12) 0.0155(12) 0.0154(11) C14 0.0645(18) 0.0324(12) 0.073(2) 0.0121(13) 0.0271(16) 0.0170(12) C15 0.0666(19) 0.0263(11) 0.0589(18) -0.0005(11) 0.0207(14) 0.0012(11) C16 0.0486(14) 0.0293(11) 0.0412(13) -0.0015(9) 0.0113(11) -0.0008(9) C17 0.0365(10) 0.0281(9) 0.0261(10) 0.0043(7) 0.0116(8) 0.0058(8) C18 0.0289(11) 0.0562(17) 0.069(2) 0.0140(15) -0.0055(12) 0.0061(11) C20 0.0229(8) 0.0244(8) 0.0209(8) 0.0025(7) 0.0012(6) -0.0021(6) C21 0.0266(9) 0.0273(9) 0.0243(9) 0.0013(7) -0.0015(7) -0.0042(7)

207

C22 0.0300(9) 0.0234(8) 0.0201(8) 0.0023(7) 0.0003(7) -0.0027(7) C23 0.0398(11) 0.0261(9) 0.0248(9) -0.0021(7) 0.0005(8) -0.0015(8) C24 0.0422(12) 0.0311(10) 0.0263(10) -0.0007(8) 0.0078(9) 0.0067(8) C25 0.0294(10) 0.0352(10) 0.0324(11) 0.0034(8) 0.0065(8) 0.0048(8) C26 0.0256(9) 0.0308(9) 0.0243(9) 0.0015(7) 0.0013(7) -0.0012(7) C27 0.0253(8) 0.0214(8) 0.0188(8) 0.0033(6) 0.0011(6) -0.0014(6) C28 0.0349(12) 0.0472(14) 0.0369(13) -0.0111(10) -0.0045(10) -0.0104(10) C30 0.0284(9) 0.0255(9) 0.0206(8) 0.0064(7) 0.0046(7) -0.0034(7) C31 0.0357(10) 0.0253(9) 0.0267(10) 0.0050(7) 0.0050(8) -0.0014(8) C32 0.0384(11) 0.0327(11) 0.0356(12) 0.0088(9) 0.0078(9) 0.0074(9) C33 0.0329(11) 0.0481(13) 0.0359(12) 0.0132(10) -0.0004(9) 0.0043(9) C34 0.0351(11) 0.0443(12) 0.0257(10) 0.0102(9) -0.0039(8) -0.0052(9) C35 0.0342(10) 0.0313(9) 0.0173(8) 0.0064(7) 0.0030(7) -0.0038(8) C60 0.050(3) 0.042(4) 0.040(3) 0.001(2) -0.003(3) 0.008(4) C61 0.059(4) 0.042(3) 0.045(3) 0.005(3) -0.001(3) -0.002(3) C62 0.040(3) 0.049(3) 0.048(3) 0.003(2) -0.001(2) 0.002(2) C63 0.045(3) 0.043(3) 0.042(3) -0.009(3) 0.000(2) -0.005(3) C64 0.044(5) 0.049(5) 0.045(3) -0.003(2) 0.005(2) -0.003(3) C65 0.031(2) 0.045(3) 0.048(3) -0.002(2) -0.003(2) 0.0021(19) C66 0.059(4) 0.036(4) 0.097(7) 0.002(4) -0.007(4) -0.012(4)

_geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Zr1 N3 2.0060(17) . ? Zr1 N1 2.1109(17) . ? Zr1 N2 2.1597(16) . ? Zr1 C3 2.4346(18) . ? Zr1 C4 2.4795(19) . ? Zr1 C30 2.4903(18) . ? Zr1 C5 2.501(2) . ? Zr1 C35 2.5400(19) . ? Zr1 C8 2.6961(19) . ?

208

Zr1 H8B 2.37(3) . ? N1 C17 1.386(3) . ? N1 C10 1.404(3) . ? N2 C27 1.386(2) . ? N2 C20 1.409(2) . ? N3 C6 1.463(3) . ? N3 C8 1.467(3) . ? C1 C20 1.507(3) . ? C1 C10 1.516(3) . ? C1 C2 1.574(3) . ? C1 H1 0.98(2) . ? C2 C3 1.509(3) . ? C2 H2A 0.95(3) . ? C2 H2B 0.99(3) . ? C3 C4 1.423(3) . ? C3 C30 1.436(3) . ? C4 C5 1.401(3) . ? C4 H4 0.97(3) . ? C5 C35 1.431(3) . ? C5 H5 0.96(3) . ? C6 C7 1.508(4) . ? C6 H6A 0.95(3) . ? C6 H6B 0.92(3) . ? C7 H7A 0.94(4) . ? C7 H7B 1.02(5) . ? C7 H7C 0.98(5) . ? C8 C9 1.513(3) . ? C8 H8A 0.95(3) . ? C8 H8B 1.00(3) . ? C9 H9A 0.98(3) . ? C9 H9B 0.95(3) . ? C9 H9C 0.94(3) . ? C10 C11 1.371(3) . ? C11 C12 1.435(3) . ? C11 C18 1.497(4) . ? C12 C17 1.412(3) . ? C12 C13 1.412(3) . ? C13 C14 1.382(5) . ? C13 H13 0.97(4) . ? C14 C15 1.389(5) . ? C14 H14 0.96(4) . ? C15 C16 1.387(4) . ? C15 H15 0.86(3) . ? C16 C17 1.394(3) . ? C16 H16 0.89(3) . ? C18 H18C 0.93(5) . ?

209

C18 H18B 0.90(5) . ? C18 H18A 1.03(7) . ? C20 C21 1.372(3) . ? C21 C22 1.433(3) . ? C21 C28 1.498(3) . ? C22 C23 1.401(3) . ? C22 C27 1.417(3) . ? C23 C24 1.388(3) . ? C23 H23 0.93(3) . ? C24 C25 1.398(3) . ? C24 H24 0.93(3) . ? C25 C26 1.387(3) . ? C25 H25 0.95(3) . ? C26 C27 1.399(3) . ? C26 H26 0.94(3) . ? C28 H28A 0.95(4) . ? C28 H28B 0.97(4) . ? C28 H28C 0.89(4) . ? C30 C31 1.426(3) . ? C30 C35 1.440(3) . ? C31 C32 1.361(3) . ? C31 H31 0.89(3) . ? C32 C33 1.424(4) . ? C32 H32 0.91(3) . ? C33 C34 1.360(4) . ? C33 H33 1.00(3) . ? C34 C35 1.422(3) . ? C34 H34 0.92(3) . ? C60 C60 0.693(11) 6_474 ? C60 C61 0.781(7) 6_474 ? C60 C65 1.405(8) . ? C60 C61 1.420(10) . ? C60 C65 1.723(8) 6_474 ? C60 C62 1.775(8) 6_474 ? C61 C60 0.781(7) 6_474 ? C61 C62 1.391(9) . ? C61 C65 1.755(9) 6_474 ? C62 C66 1.162(12) 6_474 ? C62 C63 1.360(10) . ? C62 C65 1.488(8) 6_474 ? C62 C60 1.775(8) 6_474 ? C63 C66 0.598(8) 6_474 ? C63 C65 1.118(9) 6_474 ? C63 C64 1.415(9) . ? C63 C64 1.985(9) 6_474 ? C64 C64 0.606(9) 6_474 ?

210

C64 C65 1.060(8) 6_474 ? C64 C65 1.385(7) . ? C64 C63 1.985(9) 6_474 ? C64 C66 1.987(10) 6_474 ? C65 C64 1.060(8) 6_474 ? C65 C63 1.118(9) 6_474 ? C65 C65 1.436(11) 6_474 ? C65 C62 1.488(8) 6_474 ? C65 C66 1.526(9) . ? C65 C60 1.723(8) 6_474 ? C65 C61 1.755(9) 6_474 ? C66 C63 0.598(8) 6_474 ? C66 C62 1.162(12) 6_474 ? C66 C64 1.987(10) 6_474 ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag N3 Zr1 N1 111.61(7) . . ? N3 Zr1 N2 122.58(6) . . ? N1 Zr1 N2 91.62(6) . . ? N3 Zr1 C3 143.66(7) . . ? N1 Zr1 C3 86.54(7) . . ? N2 Zr1 C3 86.34(6) . . ? N3 Zr1 C4 116.79(7) . . ? N1 Zr1 C4 78.69(7) . . ? N2 Zr1 C4 119.00(7) . . ? C3 Zr1 C4 33.66(7) . . ? N3 Zr1 C30 121.67(7) . . ? N1 Zr1 C30 120.15(6) . . ? N2 Zr1 C30 82.09(6) . . ? C3 Zr1 C30 33.88(6) . . ? C4 Zr1 C30 54.94(7) . . ? N3 Zr1 C5 88.48(7) . . ? N1 Zr1 C5 104.38(7) . . ? N2 Zr1 C5 136.97(6) . . ? C3 Zr1 C5 55.87(7) . . ? C4 Zr1 C5 32.68(7) . . ? C30 Zr1 C5 55.24(7) . . ? N3 Zr1 C35 91.06(7) . . ? N1 Zr1 C35 132.94(7) . . ?

211

N2 Zr1 C35 110.60(6) . . ? C3 Zr1 C35 55.75(7) . . ? C4 Zr1 C35 54.26(7) . . ? C30 Zr1 C35 33.26(6) . . ? C5 Zr1 C35 32.97(7) . . ? N3 Zr1 C8 32.32(6) . . ? N1 Zr1 C8 93.50(6) . . ? N2 Zr1 C8 98.51(6) . . ? C3 Zr1 C8 175.15(7) . . ? C4 Zr1 C8 141.66(7) . . ? C30 Zr1 C8 146.35(6) . . ? C5 Zr1 C8 119.54(7) . . ? C35 Zr1 C8 121.69(6) . . ? N3 Zr1 H8B 53.8(7) . . ? N1 Zr1 H8B 81.0(6) . . ? N2 Zr1 H8B 81.5(7) . . ? C3 Zr1 H8B 162.3(7) . . ? C4 Zr1 H8B 151.3(6) . . ? C30 Zr1 H8B 153.5(6) . . ? C5 Zr1 H8B 139.8(7) . . ? C35 Zr1 H8B 141.2(6) . . ? C8 Zr1 H8B 21.5(6) . . ? C17 N1 C10 106.07(17) . . ? C17 N1 Zr1 138.10(15) . . ? C10 N1 Zr1 115.57(12) . . ? C27 N2 C20 105.40(15) . . ? C27 N2 Zr1 139.66(12) . . ? C20 N2 Zr1 114.37(12) . . ? C6 N3 C8 115.64(16) . . ? C6 N3 Zr1 143.47(14) . . ? C8 N3 Zr1 100.70(12) . . ? C20 C1 C10 115.39(16) . . ? C20 C1 C2 110.35(16) . . ? C10 C1 C2 112.40(17) . . ? C20 C1 H1 105.1(14) . . ? C10 C1 H1 105.3(14) . . ? C2 C1 H1 107.5(14) . . ? C3 C2 C1 115.09(16) . . ? C3 C2 H2A 112.3(16) . . ? C1 C2 H2A 104.7(16) . . ? C3 C2 H2B 109.6(14) . . ? C1 C2 H2B 106.0(13) . . ? H2A C2 H2B 109(2) . . ? C4 C3 C30 106.60(18) . . ? C4 C3 C2 124.79(19) . . ? C30 C3 C2 128.26(18) . . ?

212

C4 C3 Zr1 74.90(11) . . ? C30 C3 Zr1 75.19(10) . . ? C2 C3 Zr1 110.42(12) . . ? C5 C4 C3 109.93(18) . . ? C5 C4 Zr1 74.50(11) . . ? C3 C4 Zr1 71.44(10) . . ? C5 C4 H4 125.9(16) . . ? C3 C4 H4 124.0(16) . . ? Zr1 C4 H4 117.3(16) . . ? C4 C5 C35 107.85(18) . . ? C4 C5 Zr1 72.81(11) . . ? C35 C5 Zr1 75.01(11) . . ? C4 C5 H5 126.1(16) . . ? C35 C5 H5 126.0(16) . . ? Zr1 C5 H5 120.1(17) . . ? N3 C6 C7 113.4(2) . . ? N3 C6 H6A 108.3(18) . . ? C7 C6 H6A 109.4(19) . . ? N3 C6 H6B 111.2(18) . . ? C7 C6 H6B 109.4(18) . . ? H6A C6 H6B 105(3) . . ? C6 C7 H7A 109(2) . . ? C6 C7 H7B 112(3) . . ? H7A C7 H7B 107(3) . . ? C6 C7 H7C 109(3) . . ? H7A C7 H7C 119(4) . . ? H7B C7 H7C 101(4) . . ? N3 C8 C9 115.43(18) . . ? N3 C8 Zr1 46.98(9) . . ? C9 C8 Zr1 130.49(15) . . ? N3 C8 H8A 112.8(17) . . ? C9 C8 H8A 110.4(16) . . ? Zr1 C8 H8A 119.0(16) . . ? N3 C8 H8B 107.5(15) . . ? C9 C8 H8B 109.1(15) . . ? Zr1 C8 H8B 60.5(15) . . ? H8A C8 H8B 100(2) . . ? C8 C9 H9A 111.0(17) . . ? C8 C9 H9B 110.0(19) . . ? H9A C9 H9B 107(2) . . ? C8 C9 H9C 108.9(19) . . ? H9A C9 H9C 112(2) . . ? H9B C9 H9C 109(3) . . ? C11 C10 N1 111.44(18) . . ? C11 C10 C1 127.86(19) . . ? N1 C10 C1 120.65(17) . . ?

213

C10 C11 C12 106.1(2) . . ? C10 C11 C18 128.2(2) . . ? C12 C11 C18 125.8(2) . . ? C17 C12 C13 119.2(2) . . ? C17 C12 C11 107.07(18) . . ? C13 C12 C11 133.7(2) . . ? C14 C13 C12 118.4(3) . . ? C14 C13 H13 122(2) . . ? C12 C13 H13 120(2) . . ? C13 C14 C15 121.4(2) . . ? C13 C14 H14 120(2) . . ? C15 C14 H14 119(2) . . ? C16 C15 C14 121.7(3) . . ? C16 C15 H15 113(2) . . ? C14 C15 H15 125(2) . . ? C15 C16 C17 117.4(3) . . ? C15 C16 H16 121(2) . . ? C17 C16 H16 121(2) . . ? N1 C17 C16 128.8(2) . . ? N1 C17 C12 109.32(19) . . ? C16 C17 C12 121.9(2) . . ? C11 C18 H18C 108(3) . . ? C11 C18 H18B 113(3) . . ? H18C C18 H18B 105(4) . . ? C11 C18 H18A 110(3) . . ? H18C C18 H18A 83(4) . . ? H18B C18 H18A 130(4) . . ? C21 C20 N2 111.72(16) . . ? C21 C20 C1 127.24(17) . . ? N2 C20 C1 120.82(16) . . ? C20 C21 C22 106.24(17) . . ? C20 C21 C28 128.6(2) . . ? C22 C21 C28 125.15(19) . . ? C23 C22 C27 120.02(18) . . ? C23 C22 C21 133.29(19) . . ? C27 C22 C21 106.66(16) . . ? C24 C23 C22 118.7(2) . . ? C24 C23 H23 122.6(16) . . ? C22 C23 H23 118.6(16) . . ? C23 C24 C25 120.8(2) . . ? C23 C24 H24 120.2(16) . . ? C25 C24 H24 118.8(16) . . ? C26 C25 C24 121.5(2) . . ? C26 C25 H25 119.9(18) . . ? C24 C25 H25 118.5(18) . . ? C25 C26 C27 118.09(19) . . ?

214

C25 C26 H26 122.2(15) . . ? C27 C26 H26 119.6(15) . . ? N2 C27 C26 129.21(17) . . ? N2 C27 C22 109.95(16) . . ? C26 C27 C22 120.80(17) . . ? C21 C28 H28A 112(2) . . ? C21 C28 H28B 110(2) . . ? H28A C28 H28B 106(3) . . ? C21 C28 H28C 113(3) . . ? H28A C28 H28C 116(4) . . ? H28B C28 H28C 98(3) . . ? C31 C30 C3 132.87(19) . . ? C31 C30 C35 119.00(19) . . ? C3 C30 C35 108.05(17) . . ? C31 C30 Zr1 117.22(13) . . ? C3 C30 Zr1 70.93(10) . . ? C35 C30 Zr1 75.27(11) . . ? C32 C31 C30 118.7(2) . . ? C32 C31 H31 121.9(17) . . ? C30 C31 H31 119.4(17) . . ? C31 C32 C33 122.0(2) . . ? C31 C32 H32 120.5(17) . . ? C33 C32 H32 117.5(17) . . ? C34 C33 C32 121.2(2) . . ? C34 C33 H33 119.8(18) . . ? C32 C33 H33 119.0(18) . . ? C33 C34 C35 118.6(2) . . ? C33 C34 H34 123.9(19) . . ? C35 C34 H34 117.5(19) . . ? C34 C35 C5 132.2(2) . . ? C34 C35 C30 120.4(2) . . ? C5 C35 C30 107.40(18) . . ? C34 C35 Zr1 121.49(14) . . ? C5 C35 Zr1 72.02(11) . . ? C30 C35 Zr1 71.48(10) . . ? C60 C60 C61 149.1(9) 6_474 6_474 ? C60 C60 C65 105.3(3) 6_474 . ? C61 C60 C65 103.1(8) 6_474 . ? C60 C60 C61 16.4(5) 6_474 . ? C61 C60 C61 136.4(10) 6_474 . ? C65 C60 C61 120.2(5) . . ? C60 C60 C65 51.9(3) 6_474 6_474 ? C61 C60 C65 154.3(9) 6_474 6_474 ? C65 C60 C65 53.5(4) . 6_474 ? C61 C60 C65 67.1(4) . 6_474 ? C60 C60 C62 157.4(6) 6_474 6_474 ?

215

C61 C60 C62 48.8(7) 6_474 6_474 ? C65 C60 C62 54.3(3) . 6_474 ? C61 C60 C62 173.7(6) . 6_474 ? C65 C60 C62 107.1(4) 6_474 6_474 ? C60 C61 C62 106.2(8) 6_474 . ? C60 C61 C60 14.5(5) 6_474 . ? C62 C61 C60 119.5(6) . . ? C60 C61 C65 51.2(6) 6_474 6_474 ? C62 C61 C65 55.0(4) . 6_474 ? C60 C61 C65 64.7(4) . 6_474 ? C66 C62 C63 26.0(4) 6_474 . ? C66 C62 C61 143.5(7) 6_474 . ? C63 C62 C61 120.5(6) . . ? C66 C62 C65 69.1(5) 6_474 6_474 ? C63 C62 C65 45.9(4) . 6_474 ? C61 C62 C65 75.0(5) . 6_474 ? C66 C62 C60 118.8(6) 6_474 6_474 ? C63 C62 C60 95.8(5) . 6_474 ? C61 C62 C60 25.0(3) . 6_474 ? C65 C62 C60 50.1(3) 6_474 6_474 ? C66 C63 C65 122.7(17) 6_474 6_474 ? C66 C63 C62 58.2(15) 6_474 . ? C65 C63 C62 73.1(5) 6_474 . ? C66 C63 C64 159.6(17) 6_474 . ? C65 C63 C64 47.7(4) 6_474 . ? C62 C63 C64 120.2(6) . . ? C66 C63 C64 153.2(16) 6_474 6_474 ? C65 C63 C64 42.5(4) 6_474 6_474 ? C62 C63 C64 115.5(5) . 6_474 ? C64 C63 C64 7.1(5) . 6_474 ? C64 C64 C65 109.4(7) 6_474 6_474 ? C64 C64 C65 46.2(6) 6_474 . ? C65 C64 C65 70.5(6) 6_474 . ? C64 C64 C63 156.2(18) 6_474 . ? C65 C64 C63 51.3(5) 6_474 . ? C65 C64 C63 121.0(6) . . ? C64 C64 C63 16.7(13) 6_474 6_474 ? C65 C64 C63 102.0(5) 6_474 6_474 ? C65 C64 C63 33.0(3) . 6_474 ? C63 C64 C63 153.3(6) . 6_474 ? C64 C64 C66 150.8(18) 6_474 6_474 ? C65 C64 C66 49.4(5) 6_474 6_474 ? C65 C64 C66 119.8(6) . 6_474 ? C63 C64 C66 6.0(5) . 6_474 ? C63 C64 C66 150.6(5) 6_474 6_474 ? C64 C65 C63 81.0(6) 6_474 6_474 ?

216

C64 C65 C64 24.4(4) 6_474 . ? C63 C65 C64 104.5(6) 6_474 . ? C64 C65 C60 139.5(7) 6_474 . ? C63 C65 C60 136.1(7) 6_474 . ? C64 C65 C60 118.4(5) . . ? C64 C65 C65 65.4(4) 6_474 6_474 ? C63 C65 C65 145.2(5) 6_474 6_474 ? C64 C65 C65 44.1(4) . 6_474 ? C60 C65 C65 74.7(3) . 6_474 ? C64 C65 C62 141.0(6) 6_474 6_474 ? C63 C65 C62 61.0(5) 6_474 6_474 ? C64 C65 C62 165.3(5) . 6_474 ? C60 C65 C62 75.7(4) . 6_474 ? C65 C65 C62 148.6(4) 6_474 6_474 ? C64 C65 C66 98.8(7) 6_474 . ? C63 C65 C66 19.3(6) 6_474 . ? C64 C65 C66 120.9(6) . . ? C60 C65 C66 120.6(6) . . ? C65 C65 C66 164.1(5) 6_474 . ? C62 C65 C66 45.3(5) 6_474 . ? C64 C65 C60 116.9(6) 6_474 6_474 ? C63 C65 C60 156.5(6) 6_474 6_474 ? C64 C65 C60 95.7(4) . 6_474 ? C60 C65 C60 22.8(4) . 6_474 ? C65 C65 C60 51.9(3) 6_474 6_474 ? C62 C65 C60 98.1(4) 6_474 6_474 ? C66 C65 C60 143.3(6) . 6_474 ? C64 C65 C61 161.1(7) 6_474 6_474 ? C63 C65 C61 110.6(6) 6_474 6_474 ? C64 C65 C61 143.9(5) . 6_474 ? C60 C65 C61 25.7(3) . 6_474 ? C65 C65 C61 99.8(3) 6_474 6_474 ? C62 C65 C61 50.0(4) 6_474 6_474 ? C66 C65 C61 95.1(6) . 6_474 ? C60 C65 C61 48.2(3) 6_474 6_474 ? C63 C66 C62 95.8(16) 6_474 6_474 ? C63 C66 C65 38.0(12) 6_474 . ? C62 C66 C65 65.6(6) 6_474 . ? C63 C66 C64 14.4(12) 6_474 6_474 ? C62 C66 C64 96.1(6) 6_474 6_474 ? C65 C66 C64 31.8(3) . 6_474 ?

_diffrn_measured_fraction_theta_max 0.997 _diffrn_reflns_theta_full 26.00 _diffrn_measured_fraction_theta_full 0.999 _refine_diff_density_max 0.644

217

_refine_diff_density_min -0.285 _refine_diff_density_rms 0.103

218