View Considers the IR Spectra of Such Complexes Was Done to Examine the Structure of These Complexes in 1982.31 for Example, It Was Observed That The

JOANNA M. BERES

A Dissertation

Presented to

The Graduate Faculty of The University of Akron

In Partial Fulfillment

of the Requirements for the Degree

Doctor of Philosophy

Joanna M. Beres

August, 2011 REACTIONS OF SILANES AND CHLOROPHOSPHAZENES WITH HMPA

Joanna M. Beres

Dissertation

Approved: Accepted:

______Advisor Department Chair Dr. Claire A. Tessier Dr. Kim C. Calvo

______Committee Member Dean of the College Dr. Wiley J. Youngs Dr. Chand Midha

______Committee Member Dean of the Graduate School Dr. Matthew P. Espe Dr. George R. Newkome

______Committee Member Date Dr. Peter L. Rinaldi

______Committee Member Dr. Li Jia

ABSTRACT

The reaction of Si(IV) or P(V) fragments with HMPA will be shown to produce cationic species. Nonmetallic, cationic elements at higher valency are known as onium ions. These onium ions are often highly reactive intermediates.

Therefore, we studied them to better understand the synthetic routes in which they are suspected to play a role in. The use of a metal-assisted route will be explored for the formation of siliconium and phosphonium species.

The reaction of M(CO)5HMPA with SiR3H in benzene produces a cationic species stabilized by a weakly coordination anion in a liquid clathrate matrix when M is a group six transition metal. The reaction utilizes a one-pot synthesis.

The hydrido silanes have been used in this reaction to form stable siliconium

+ + cations [SiR3(HMPA) ] or [SiR3(HMPA)2 ] that have been proposed intermediates in several organic syntheses. This general synthesis produces a liquid clathrate

- through the presence of the weakly coordination anion [(CO)5MHM(CO)5 ]. This anion’s specific geometry seems to be crucial to the formation of the liquid clathrate and therefore the stabilization of the cations. In order to obtain X-ray crystallographic data of the cation an ion exchange reaction was conducted

iii

+ - + - between [SiEt3(HMPA) ][H(W(CO)5)2 ] and K [B(C6F5)4) ]. X-ray crystallographic

+ + data was obtained for the [SiEt3(HMPA) ][B(C6F5)4 ] complex. Mass

+ spectrometry was showed the ions [SiEt3(HMPA) ]

- + - an [HW2(CO)8 ] for [SiEt3(HMPA) ][H(W(CO)5)2 ]. However, mass spectrometric

+ - characterization of [SiH2Ph(HMPA)2 ][H(W(CO)5)2 ] showed presence of the

[SiPhH(HMPA)Na+] cation due to the sensitivity of the compound. The

+ decreased stability of the [SiH2Ph(HMPA)2 ] cation is due to the high reactivity of the silicon-hydrogen bond as well as the tendency for five-coordinate silicon compounds to be highly reactive. The generality of this synthesis was investigated and the products were characterized by multi nuclear NMR, ESI-MS and X-ray crystallography.

This same metal assisted route was unsuccessful in producing the desired

+ phosphonium cation [P3N3Cl5(HMPA) ] from [PCl2N]3. This cation is similar to a proposed intermediate in the ring-opening polymerization of [PCl2N]3. However, the reaction of HMPA with a variety of different cyclic chlorophosphazenes was

+ found to form a different phosphonium cation, [P(NMe2)3Cl ]. A general oxygen/chlorine transfer reaction was observed between the chlorophosphazenes and HMPA resulting in oxygen containing anions. A reaction with minimal byproducts was established for [PCl2N]3 and [PCl2N]4 with

+ - HMPA resulting in the cationic species [P(NMe2)3Cl ][P3N3Cl5O ] and

+ - [P(NMe2)3Cl ][P4N4Cl7O ] respectively. The generality of the reaction of

chlorophosphazenes with HMPA was investigated. The products were characterized by multinuclear NMR, ESI-MS and X-ray crystallography.

ACKNOWLEDGEMENTS

First and foremost I must thank my research advisor, Dr. Claire Tessier, for her amazing guidance throughout these past five years. Her general thirst for knowledge is contagious and her intelligence is inspiring. The many late nights that she spent working with me are the only reason that I have made it where I am today. Above all she is a kind, understanding woman whose friendship I will always cherish. Thank you to my committee members: Dr. Youngs, Dr. Espe,

Dr. Rinaldi and Dr. Jia for their guidance in this work. Thank you to Dr.

Christopher Allen for the donation of [PCl2N]4 to the Tessier laboratory. Thank you to Boulder Scientific for the donation of K[B(C6F5)4].

I would also like to thank my friends. Zin-Min, Dave and Nick have made seemingly dull times in the lab a joy. I will miss all of our conversations over science as well as our laughs over everything else. Anna, I am so thankful that life has brought us back together again. It has been such a comfort having her by my side through this whole experience. I am truly lucky to call her my friend.

Thank you also to those teachers who have led me to this point in my life.

First, thank you to my parents for being the first teachers of my life. They have

taught me to value education, to value relationships and to always have faith.

Their love and support has meant more to me than they will ever know. Thank you to Mrs. Budd for introducing me to science and giving me the confidence to pursue it. Thank you to Mr. Brovarone for seeing my aptitude for chemistry and challenging me to think beyond the classroom. Thank you to Dr. Walsh and Dr.

Freeland for introducing the possibility of graduate school into my future; without their confidence I would not have thought it was possible.

Last, but in no way the least, thank you to my husband. Nate has been my rock throughout these past years. I would have never been able to finish this work if it was not for his love and support. He will never know how much I depend on his guidance and companionship.

vii

DEDICATION

to my parents for giving me the tools to complete this degree

to my husband for keeping me sane in the process

viii

TABLE OF CONTENTS

Page

LIST OF TABLES ...... x

LIST OF FIGURES ...... xi

CHAPTER

I. INTRODUCTION ...... 1

II. SILICONIUM CATIONS IN A LIQUID CLATHRATE MEDIA ...... 3

2.1 Introduction ...... 3

2.2 Experimental ...... 28

2.3 Results and Discussion ...... 35

III. REACTIONS OF CHLOROPHOSPHAZENES WITH HMPA ...... 55

3.1 Introduction ...... 55

3.2 Experimental ...... 74

3.3 Results and Discussion ...... 81

IV. CONCLUSION ...... 103

REFERENCES ...... 105

APPENDIX ...... 114

LIST OF TABLES

Table Page

2.1 X-ray crystal data of [SiEt3HMPA][B(C6F5)4] and W(CO)4(HMPA)2 ...... 33

- 2.2 IR values for [(M(CO)5)2X , BLC = benzene liquid clathrate ...... 42

o 2.3 Selected bond distances (Å) and angles ( ) of W(CO)4(HMPA)2 ...... 49

+ - 3.1 X-ray crystal structure data of [P(NMe2)3Cl ][P3N3Cl5O ],

+ - + - + - [P(NMe2)3Cl ][P4N4Cl7O ]. [P(NMe2)3Cl ][B(C6F5)4 ] and [P(NMe2)3Cl ]Cl ... 79

3.3 Selection of bond lengths (Å) and bond angles (o) for

+ - [P(NMe2)3Cl ][P3N3Cl5O ] ...... 98

+ 3.4 Selected bond lengths (Å) for [P(NMe2)3Cl ] ...... 101

LIST OF FIGURES

Figure Page

1.1 Examples of siliconium and phosphonium cations ...... 2

2.1 The changing geometry and hybridization of silicon as the coordination

number increases ...... 8

2.2 Depiction of the combination of three sp2 orbitals and a p orbital for five-

coordinate SiR4L ...... 11

2.3 Simple MO diagram for trigonal bypyramidal molecules such as PF5.

Adapted from ref. 13 ...... 12

2.4 Examples of chiral base promoters synthesizes by Denmark ...... 15

2.5 Suspected six-membered ring transition state ...... 16

2.6 Possible siliconium or neutral intermediates for Equation 2.2 adapted from

ref 21...... 18

. 2.7 Ball and stick plot of trans SiCl4 2HMPA from ref. 22 ...... 19

. + - 2.8 Ball and stick model of [SiCl3 3HMPA ] HCl2 from ref. 22...... 20

- 2.9 Examples of linear and bent geometry of [H(W(CO)5)2 ] ...... 21

2.10 Representation of a liquid clathrate with excess aromatic ...... 22

+ - 2.11 The interaction sites available for the K cation to the N3 anion in KN3,

+ KN3(AlMe3) and KN3(AlMe3)2.As the steric hindrance increases, the K

cation has fewer possible sites for interaction with the anion...... 23

2.12 Two dimensional model of a liquid clathrate adapted from ref. 28 ...... 24

+ - 2.13 Ball and stick model of [SiCl3(HMPA)3 ] [SiCl3Fe(CO)4 ] from ref. 29 ...... 26

+ 2.14 Isotropic drawing of the crystal structure of SiPhH(HMPA)3 (H was not found) from ref 34 ...... 39

+ - 2.15 Thermal ellipsoid plot of [SiEt3(HMPA) ][B(C6F5)4 ] at a 50% ...... 40

+ 2.16 ESI-MS [SiEt3HMPA ], experimental (left) and theoretical (right) ...... 44

- 2.17 ESI-MS negative mode of [HW2(CO)8 ], experimental (left) theoretical

(right) ...... 44

2.18 ESI-MS negative mode showing loss of carbonyl ligands (experimental) .... 45

2.19 Theoretical isotopic distribution of compounds of [HW2(CO)6],

HW2(CO)4THF, HW2(CO)7 and HW2(CO)8 ...... 45

+ 2.20 Mass spectrum of [SiEt3(HMPA) ]. Experimental (left) theoretical (right) ..... 46

- 2.21 ESI-MS negative mode of [B(C6F5)4 ] experimental (left) theoretical (right) . 46

1 - 2.22 H NMR spectrum of the tungsten-hydride resonance of the [H(W(CO)5)2 ]

anion ...... 47

2.23 Thermal ellipsoid plot of W(CO)4(HMPA)2 at 50% probability ...... 49

+ - 2.24 Thermal ellipsoid plot of [SiEt3(HMPA) ][B(C6F5)4 ] with 50% probability ..... 49

+ 2.25 Thermal Ellipsoid plot of [SiEt3(HMPA) ] at 50% probability ...... 52

3.1 Examples of common phosphazenes ...... 56

xii

3.2 HMPA stabilized phosphonium cation ...... 61

3.3 Adduct formation from the reaction of [PCl2N]3 with AlCl3, GaCl3 and

SbCl5 ...... 62

3.4 Tautomers of P3N3Cl5OH ...... 68

3.5 Multiple bond drawing of [PCl2N]3 (left) zwitterion model of [PCl2N]3

(right) ...... 72

3.6 EPR spectrum taken at 4.2 K of the radical product (g⸗ = 1.93, g┴ = 1.76),

W(CO)5Cl) from the reaction in Equation 3.12 in benzene ...... 83

+ 3.7 EPR spectrum taken at 4.2 K of the radical product (g = 1.97), Cr(CO)6 )

of the reaction of [PCl2N]3 and Cr(CO)5HMPA in benzene...... 83

+ - 3.8 Thermal ellipsoid plot of [P(NMe2)3Cl ][B(C6F5)4 ] at 50% probability ...... 84

31 6 3.9 P spectrum of the reaction of [PCl2N]3 with HMPA in d benzene after 1

h. The different phosphorus atoms are identified by letters ...... 87

31 6 3.10 P spectrum of the reaction of [PCl2N]4 with HMPA in d benzene after 4

h. The different phosphorus atoms are identified by letters...... 89

3.11 Expansion region from -7.5 ppm to .22.8 ppm of the 31P spectrum in Fig.

- 3.10 showing resonances of the [P4N4Cl7O ] anion. The different

phosphorus atoms are identified by letters...... 89

31 6 3.12 P spectrum of the reaction of [PCl2N]m with excess HMPA in d benzene

after 4h...... 91

xiii

3.13 Expansion of the 31P spectrum in Fig 3.12 showing resonances of the

phosphazene anions ...... 91

+ + - 3.14 Positive mode ESI-MS of [P(NMe2)3Cl ] in [P(NMe2)3Cl ][P3N3Cl5O ]

experimental (left) and theoretical (right) ...... 92

- + - 3.15 Negative mode ESI-MS of [P3N3Cl5O ] in [P(NMe2)3Cl ][P3N3Cl5O ]

experimental (left) and theoretical (right) ...... 93

+ + - 3.16 Positive mode ESI-MS of [P(NMe2)3Cl ] cation in [P(NMe2)3Cl ][P4N4Cl7O ]

(left) and theoretical (right) ...... 94

- + - 3.17 Negative mode ESI-MS of [P4N4Cl7O ] anion in [P(NMe2)3Cl ][P4N4Cl7O ]

experimental (left) and theoretical (right) ...... 94

+ - 3.18 Thermal ellipsoid plot of the crystal structure of [P(NMe2)3 ][P3N3Cl5O ] at

50% probability ...... 96

- 3.19 Thermal ellipsoid plot of [P3N3Cl5O ] from the unit cell of

+ - [P(NMe2)3Cl ][P3N3Cl5O ] with a 50% probability ...... 97

- 3.20 Thermal ellipsoid plot of the crystal structure of [P(NMe2)3Cl ][P4N4Cl7O .... 98

- 3.21 Thermal ellipsoid plot of the [P4N4Cl7O ] anion from the crystal structure of

+ - [P(NMe2)3Cl ][P4N4Cl7O ] ...... 99

+ 3.4 Thermal ellipsoid plots of the [P(NMe2)3Cl ] cations from the crystal

+ - + - structures of [P(NMe2)3Cl ][P4N4Cl7O ] (left) and [P(NMe2)3Cl ][P3N3Cl5O ]

(right) at 50% probability...... 100

xiv

CHAPTER I

INTRODUCTION

1.1 General Introduction and Goals

Onium ions are positively charged compounds of nonmetallic elements at higher valency. A few examples of these ions include azonium, oxonium and sulfonium ions.1 The goal of this research is to study siliconium and phosphonium ions stabilized by HMPA, hexamethylphosphoramide, as shown in

Figure 1.1. As with most onium ions, the siliconium and phosphonium ions are proposed intermediates in highly studied synthetic reactions like the allylation of aldehydes and the ring opening polymerization of cyclic chlorophosphazenes.2, 3

There was also a general interest in using phosphorus and silicon to find compounds analogous to the carbocations, as well as inducing more metallic behavior in silicon and phosphorus.4 Isolation of a phosphorus or silicon cation analogous to carbocations was generally found to be impractical and therefore the study of higher coordination cations was studied more exstensively.

Me2N NMe2

P NMe2 Cl O R HMPA R P HMPA Si R N N R Si R Cl2P PCl2 y R HMPA N

y = 1, 2 or more Figure 1.1 Examples of siliconium and phosphonium cations

The initial plan for this research was to use a metal assisted reaction to isolate onium ions of both silicon and phosphorus. This was successful in the case of the siliconium cations. The strategy behind the use of metal-assisted routes was two-fold (1) to allow for milder synthetic conditions and (2) to form weakly coordinating anions from the metal fragments that might stabilize the cations. In some cases, the metal-assisted route was useful. In others, metal- based radicals formed which were undesired. In these later cases, synthetic routes that did not involve metal-assistance were used.

CHAPTER II

Siliconium Cations in a Liquid Clathrate Media

2.1 Introduction

The goal of this project was the reinvestigation of the synthesis and the

+ - further characterization of [SiR3(HMPA)1or2 ][H(W(CO)5)2 ] which contain base stabilized siliconium cations. Section 2.1.1 will discuss the chemistry at silicon vs. carbon, to understand the unique chemistry of silicon explained through its bonding and coordination number. Various examples of silicon cations will be described including three coordinate cations, silylium cations, as well as cations of a larger coordination number, siliconium cations. We believe that a possible transition state for these compounds will be the formation of a metal-silicon bond.

Therefore, similar compounds with be discussed in Section 2.1.7. Organic

- applications for related siliconium cations with anions other than [H(W(CO)5)2 ] will be presented including their role in the allylation of aldehydes. A major

+ - reason we have reinvestigated [SiR3(HMPA)1or2 ][H(W(CO)5)2 ] was to develop a simpler synthesis, one that might be more useful to the organic chemist.

The synthesis of these siliconium cations was accomplished via a metal

- assisted process that gives the [H(W(CO)5)2 ] anion. Group six bridging hydride anions have been well known for nearly fifty years, and their synthesis and applications will be discussed in Section 2.1.6. The

+ - [SiR3(HMPA)1or2 ][H(W(CO)5)2 ] compounds prepared in benzene are initially

- obtained as liquid clathrates. The geometry of the [H(W(CO)5)2 ] anion is similar

- to the geometry of the first anion observed to form liquid clathrates, [N3(AlMe3)2 ],

This unique geometry is believed to cause the formation of liquid clathrates in this chemistry. Therefore, the historical discovery of liquid clathrates as a guest- host matrix in liquid phase will also be discussed in Section 2.1.8.

2.1.1 Coordination number of silicon

Silicon has been a very interesting tool for organic chemists. Silicon’s important differences between its group fourteen complement, carbon, make it useful in the formation of carbon-carbon bonds.5, 6 Most organosilicon compounds are four coordinate but silicon also has the ability to be five or six coordinate. This differs from carbon, which is generally no more than four coordinate in stable compounds and only becomes five coordinate as an intermediate.6 Organosilicon complexes are also of interest because of their high reactivites and special biological activites.5 The chemical differences of carbon

versus silicon can largely be explained by their differences in atomic radius and electronegativity. Carbon and silicon have atomic radii of 77 pm and 111 pm, respectively. This difference accounts for a slightly weaker silicon-silicon bond

(340 kJ/mol) than the carbon-carbon bond (368 kJ/mol).7 This trend can also be observed when carbon or silicon is bonded with hydrogen, which results in silicon-hydrogen bonds being generally less stable than those with carbon- hydrogen bonds.7 Silicon is also significantly less electronegative than carbon,

1.92 and 2.54 respectively.7 Therefore, when silicon is bound to hydrogen, which has an electronegativity of 2.20, it becomes more susceptible to nucleophilic attack than the carbon-hydrogen bond.7 The increased atomic radius of silicon also provides a greater possibility for attack by nucleophiles simply based on increased surface area.7 All of these differences between carbon and silicon account for the unique chemistry at silicon.

2.1.2 Silicon cations

There are a few general routes to silicon cations as is shown in Scheme

2.1. The first method involves the removal of a hydride from SiR3H by the

8 + triphenylcarbenium cation. In some cases, this route gives SiR3 that have only weak interactions to a fourth species. The other two methods involve base- induced ionization of a silyl halide or cleavage of a metal-silicon bond that will

+ 1,9 yield [SiR3(base)n ] (base = nitrogen or oxygen base). These latter two

methods always give cations that have strong Si-base interactions and coordination numbers 4-6 at silicon. For all routes in Scheme 2.1 the coordination number at silicon depends on steric hindrance of the R groups, coordination of the anion to the cation and the nature of the solvent and base.

+ [SiR3 ][X ] + CPh3H + SiR3H + [CPh3 ][X ] + base [SiR3(base)n ][X ] + CPh3H

+ [SiR3(base)n ][X ]

SiR3X + n base n = 1 or 2

SiR3X(base)n

+ M(L)m(SiR3) + n(base) [SiR3(base)n ][M(L)m ] n = 1 or 2

Scheme 2.1. Synthetic routes for silicon cations

The ability of silicon to have coordination numbers greater than four is in contrast to the ability of carbon to obtain lower coordination numbers.7 There has

+ been general interest in stabilizing a silylium cation (SiR3 ), which is the silicon

+ 7 analogue of the carbenium ion (R3C ), in the condensed phase. There are multiple issues with the survival of silylium cations,10, 11 the first being that the increased coordination area of silicon causes a tendency to be four, five or six coordinate rather than three. Also, because of its lower electronegativity, silicon has a greater tendency to hold the positive charge rather than distributing it to its substituents.10, 11 Another challenge to overcome is that the traditional methods

used to prepare carbocations are not suitable for the synthesis of silylium cations due to silicon’s high affinity for oxygen, fluorine, and chlorine.12 Therefore, upon generation of silylium cations they tend to quickly form a four or five coordinate complex with solvent molecules or the anion, referred to as solvated silylium cations or siliconium cations.12 This increased coordination results in the loss of silylium character and formation of siliconium cations. As a result, successful synthesis of a silylium cation in the condensed phase must involve: a very weakly coordinating anion (WCA), a weakly coordinating solvent and optimal stabilization of the substituents.10, 11 There have been reports of free silylium cations in solution characterized by a downfield shift in the 29Si NMR spectrum

- 12 near 220 ppm, through the use of bulky substituents and the WCA B(C6F5)4 .

Recently, Lambert et al.9 has reported the first crystallographic evidence of a free

. silylium ion [(Mes)3Si][H-CB11Me5Br6] C6H6. This silylium cation is stabilized by the steric hindrance of the mesityl groups and the WCA carborane. Both the

- - B(C6F5)4 and HCB11Me5Br6 anions are expensive, reducing the appeal of their usefulness. Although the chemistry seen through these reactions is interesting it becomes obvious that the difficulty of making these silylium ions make them impractical for use in organic applications.

2.1.3 Reactivity of Silicon

There are several useful organic reactions that involve silicon. This has prompted interest in the reaction mechanisms at silicon.6 Mechanisms of silicon 7

chemistry are usually SN2 in nature, and rarely proceed in an SN1 fashion. The most abundant form of silicon on earth is silicon dioxide, SiO2, and is clearly a very stable form of silicon. However, when silicon increases its coordination number to five, the reactivity greatly increases and this occurs even for SiO2.

When silicon has more than four substituents it is considered to be hypervalent or more accurately, hypercoordinate. Such hypervalent silicon complexes have interesting electronic effects at silicon due to the strong electron-donating inductive effect of the added basic ligand which creates a large dipole moment.5

This increased dipole can be further explained by considering the transition of four to five and five to six coordinate silicon (Fig. 2.1) with respect to coordination number and bonding.6

L R L R L R L R Si R Si R Si R R R R R R L

SiR4 SiR4L SiR4L2 Traditional 3 3 3 2 hybridizations sp sp d sp d Alternative 2 none sp sp or p only hybridizations Figure 2.1. The changing geometry and hybridization of silicon as the coordination number increases Silicon with increasing coordination numbers are shown in Figure 2.1. As the number of ligands increases, the total s character of the silicon decreases.6

These ligands are typically electron withdrawing causing a δ- charge on the

substituents and an increasingly δ+ charge on the silicon atom, thereby increasing the dipole moment.6 The magnitude of this electron density difference

6 depends on the electronegativity of the substituents. Compounds SiR4 and

SiR4L can act as Lewis acids because of their ability to accept additional ligands enhancing the metalloid character at the silicon atom. However, SiR4L2 does not act as a Lewis acid because silicon rarely will be seven or eight coordinate and

6 therefore cannot be an acceptor. The hypercoordinated complexes, SiR4 and

6 SiR4L2, have elongated bonds. This allows for enhanced capability of transferring a formally negatively charge to an acceptor, further increasing the partial negative charge at R and L.6 Therefore, mechanisms involving hypervalent silicon at the reactive site can show a transfer of a substituent resulting in the formation of a carbon-carbon bond rather than a carbon-silicon

6 bond. The tetravalent organosilicon compounds, SiR4, are not hypervalent and therefore have entirely different reactivity.6 These bonds are therefore more covalent.6 The most common use in organic synthesis for four-coordinate silicon is in transition-metal-catalyzed hydrosilylation. The silicon-hydrogen bond is very similar the hydrogen-hydrogen bond based on the electronegativity and therefore, reactions proceeds under similar reaction conditions.6

Transformations involving tetravalent silicon (SiR4) at the reactive site allow for carbon-silicon bond formation, rather than carbon-carbon bond formation.6

2.1.4 Bonding in hypercoordinate silicon

Traditional hybridization at silicon for SiR4, SiR4L and SiR4L2 are shown in

Figure 2.1. Traditional valence bond theory would tell us that for a tetrahedral molecule we should expect four sp3 hybridized orbitals, and bond angles consistent with this model are observed in four coordinate silicon compounds

(Figure 2.1).13 However, as we move to higher coordination numbers, this theory does not seem to hold up.13 When silicon is at a coordination number of five, one might typically expect a sp3d hybridization and a bond order of five. However, that would imply that the percent d character at the silicon atom should be around twenty percent. In fact, the d bonding character seems to be less than five percent through molecular orbital calculations.13 This is explained because there is too large of an energy gap between the d orbitals and the s and p orbitals of silicon for effective hybridization to occur. In addition, the bonds in SiR4L and

SiR4L2 are longer and weaker than in SiR4. Alternative bonding descriptions that do not rely on d character are needed for SiR4L and SiR4L2.

Alternative, non-d containing hybridization for SiR4L and SiR4L2 are shown in Figure 2.1. In these descriptions, normal two-electron bonds are formed by the hybrid orbitals and three-center four-electron bonds are formed by the p-

2 orbitals. For example consider SiR4L using an sp hybridization (figure 2.1) now one would see the bonding of the p orbital as being two bonding and two nonbonding electrons that delocalized in a three center four electron bond with 10

two other ligands, resulting in a bonding order of one for the p orbital and a bonding order of four for the overall complex.13 The electron deficient bonds that are formed with these electrons tend to have weaker, longer bonds than are seen with a traditional two center two electron bonding model.13 A better explanation of the bonding could be described as the combination of three sp2 hybridized orbitals and one traditional p orbital as shown in the Figure 2.2, also showing an overall bond order of four. This theory can also be used to explain the bonding of a hexavalent silicon atom with two sp orbitals and two traditional p orbitals

p p 2 2 sp sspp2 2 sp2 sp2 2 2 sp sp sp

Figure 2.2: Depiction of the combination of three sp2 orbitals and a p orbital for five-coordinate SiR4L

2a2’’

a2’’+ e’ np 2e’

3a1’

2a1’+a2’’+e’ 2a ’ σ 1 1e’ a ’ ns 1 1a ’’ 2

1a1’ A AY Y 5 5

Figure 2.3. Simple MO diagram for trigonal bypyramidal molecules such as PF5. Adapted from ref. 13.

The molecular orbital diagram for AY5 (Figure 2.3), which could represent

- SiF5 or PF5, shows that the symmetry of the ligand orbitals does not match up completely with the symmetry elements of the central atom. Of the five p orbitals of the Y atoms, only four are stabilized into bonding orbitals resulting in a pair of

13 electrons in the nonbonding 2a1’ orbital. This model also gives a bond order of four, thus, giving a better explanation than traditional hybridizations for the longer and weaker bonds of five-coordinate

2.1.5 Silicon Intermediates in Organic Synthesis

Shown in the general equation below, while using the silicon active site as a catalyst, the synthesis of homoallylic alcohols are often done through allylation or crotylation of aldehydes (Equation. 2.1).14 An enantioselective Lewis base catalyst is used to for high asymmetric induction with allyltrialkylsilanes.14

OH R1 SiLn O Base + R (Eq. 2.1) R H 2 2 R1 R R

Berrisford used chiral Lewis bases to activate stoichiometric organometallic reagents.14 This notion was used for allyltrichlorosilanes activated by oxygen- donor ligands.14 The problem with some oxygen donor ligands is that increased steric bulk causes attenuation of the rate.15 Specifically this was observed with phosphoramide ligands.14 Berrisford found that the use of ammonium salt additives could significantly improve reaction rates (Equation. 2.2).14 This was

SiCl3

1 1 OH R SiCl3 R OH

O-donor ligand O-donor ligand (Eq. 2.2) R RCHO R R1 R1

thought to be caused by the sequestering of the halide which promotes the activity.14 Therefore, the use of other salts, including silver salts, were used to precipitate silver chloride.15 The presence of these and other salts improved the reaction times from 72 h to 2 h.14 Berrisford further observed that simply having the presence of the chloride ion alone was enough to increase the rate of the reaction, which led them to believe that the presence of an ionic species is advantageous for reactivity. This notion was suspected to be possibly caused by an ionic transition state, with the triflate salt resulting in the highest yields, about

88%.14 In fact, allyltrichlorosilane in DMF was found to be 1,000 times more ionic than the same compound in dichloromethane, further demonstrating that the mechanism must involve an ionic complex.15 Another important observation about this reaction (Equation. 2.1) is that it does not proceed without the presence of an oxygen donor such as dimethylforamide (DMF) or triphenylphosphine oxide (TPPO), although these oxygen-donors could be used in substoichiometric amounts.15

At nearly the same time as Berrisfords’ work, Denmark was working on this same reaction using chiral O-donors in catalytic amounts.16 Denmark discovered that addition of hexamethylphosphoramide (HMPA, O=P(NMe2)3) to the allylation of aldehydes reaction (Equation 2.1) resulted in 100% conversion and a lessening of the reaction time to only three min.16 Denmark was interested in altering the nitrogen sites of HMPA with substituents that differ in shape and properties.2 He was able to synthesize phosphoramides with the general 14

strategy of coupling a diamine to a phosphoramide reagent as shown in Figure

2.4.2 They were successful in making enantiomerically pure N-arylamines and, therefore, able to synthesize enantiomerically pure 1,2 diamines.2 This was the first step in developing an oxygen donor with improved selectivity and reaction efficiency. Denmark suspected that the transition state involved a hexacoordinate siliconium species.16 In the literature Denmark refers to siliconium species as a siliconate species. As the suffix ―ate‖ usually implies a negative ion, this work will be using the term siliconium as establish by Olah.1

Me Me O N Ph N O N O P P P N N N N Ph N N Me Me

Figure 2.4. Examples of chiral base promoters synthesizes by Denmark16

Wang was interested in synthesizing an optically active homoallylic alcohol, but previous studies had not shown high enantioselectivity because of an open transition structure.17 Wang believed that if he could force the reaction to proceed through a six membered cyclic transition state he could improve the enantioselectivity. Kobayashi reported success in using DMF, as the base, in the

18 reaction of allyltrichlorosilanes, Si(ally)Cl3, aldehydes. The reaction proceeds via a five coordinate intermediate, Si(allyl)Cl3(DMF), with a six membered ring

transition state, shown in Figure 2.5.18 Wang suspected the Lewis base DMF coordinated to the silicon atom forming a chiral five coordinated siliconium, which

15 was previously seen complexed with Et3N. The now acidic silicon underwent nucleophilic addition to aldehydes giving-optically active homoallylic alcohols with improved enantioselectivity.17

Figure 2.5. Suspected six-membered ring transition state

Denmark investigated the structure of the transition state of these complexes.19 The key structure of the six membered, cyclic, chair-like structure was evaluated through kinetic studies.19 These studies found that the reaction was first order with respect to allyltrichlorosilane and aldehyde, but the phosphoramide reaction order was 1.77.19 The reaction order of the phosphoramide being greater than one showed that the reaction must involve two simultaneous pathways, one of which involved two HMPA molecules.19 This would require the ionization of one chlorine atom to make a six coordinate octahedral cationic species as shown in Figure 2.6.19 A reaction order of less than two implied that there must be a competing pathway with the one phosphoramide pathway. Two possibilities are shown in Figure 2.6; a 16

hexacoordinate, octahedral neutral transition state or the ionization of a chloride anion producing a cationic, trigonal bipyramidal transition.19 However, lack of a significant drop in enantioselectivity made this latter option not as likely.20

Therefore, there are two likely possibilities, first that the one phosphoramide pathway is not kinetically viable and the 1.77 reaction order is because of another reason. The second possibility is that the pathway is viable but gives rise to the same magnitude of enantioselectivity. Denmark was unable to eliminate either possibility.19 These studies suggested that the two phosphoramide pathway gave the highest selectivity and was the most effective process.19 This also explains the observation that steric bulk on the phosphoramide decreases the rate of the reaction because two bulky phosphoramides could not fit around the silicon in the two phosphoramide pathway.21

Two phosphoramide pathway + Cl- NR2 R2N P NR2 NR O 2 O O P NR2 H Si NR2 H Cl H Cl Cationic octahedron

One phosphoramide pathway + Cl- H NR2 NR Cl P 2 H NR O NR2 Cl 2 O O P NR2 H Si H Si NR2 O Cl H Cl H Cl

Neutral octahedron Cationic trigonal bipyramid Figure 2.6. Possible siliconium or neutral intermediates for equation 2.2 adapted from ref 21

These findings prompted interest in stabilizing and characterizing silicon cations in order to support, and further understand the presence of a hypervalent

22 silicon cation. Therefore, the reaction of HMPA with SiCl4 was studied. The resulting complexes were highly fluxional and were therefore studied by NMR at

-60 oC and -100 oC.22 With two equivalents of HMPA, the 29Si NMR spectrum showed a five coordinate species at -120.5 ppm that was assigned as

. + - 22 [SiCl3 2HMPA ] Cl . A six coordinate species was also observed at -205.5 ppm

. 22 and -207.8 ppm assigned as the cis and trans forms of SiCl4 2HMPA . When

the number of equivalent HMPA was increased to three another six coordinate species was observed at -210 ppm and -207 ppm were assigned as

. + - 22 [SiCl3 3HMPA ]Cl with both the fac and mer conformations present.

Although the solution NMR was convincing for the presence of a silicon cation, further studies were done in the solid state structure by way of X-ray

22 . crystallography. A crystal of trans SiCl4 2HMPA was isolated showing a near perfect octahedral center around the trans-bis HMPA complex (Figure 2.7).22 One week after the reaction, more crystals were obtained and found to be

. + - 22 [SiCl3 3HMPA ] HCl2 (Figure 2.8). This was the first X-ray diffraction crystal structure reported for an ionized Lewis base-silicon complex in the literature.22

This crystal structure was convincing evidence of the intermediates of silicon cations from Denmark’s previous work.22

. Figure 2.7. Ball and stick plot of trans SiCl4 2HMPA from ref. 22

. + - Figure 2.8. Ball and stick model of [SiCl3 3HMPA ] HCl2 from ref. 22

- 2.1.6 [H(M(CO)5)2 ] anions (M = Group 6)

- Group six bridging metal hydrides [H(M(CO)5)2 ] were first of interest in the late 1960’s because of the unique, unsupported, three center two electron bond for the bridging hydride.23 Bridging hydrides had previously been seen in borane chemistry, however, these bridging hydride typically had two or three bridging hydrides in the same molecule, thereby considered ―supported‖.23 In 1969

- [H(W(CO)5)2 ] was confirmed by NMR, however, the data were consistent with either a linear or bent conformation (Figure 2.9).23 Hayter was able to find a relatively straight forward synthesis for these anions by reacting NaBH4 with

+ - 24 W(CO)6, followed by the addition of [Ph4P ] Br . Neutron diffraction and X-ray

+ - 23 diffraction studies were conducted of [Ph4P ][H(W(CO)5)2 ]. In 1985, a list of fourteen, bridging, group six metal hydride structures were compared, with a number of different cations.23 Through this study it was found that the hydride 20

was bent in the solid state, with the staggered geometry being the most favored.23 Further work was done with bridging hydrides where the metals were two different metals also exhibiting an unsupported three center two electron bond.25 These anions although interesting individually, have been found to also be examples of weakly coordinating anions with bent geometries, similar to the aluminum containing anions discussed next in section 2.1.8 on liquid clathrates.

The most recent use of these anions has been in the formation of lanthanide clusters.26

CO CO CO CO CO CO CO H CO CO W H W CO CO W W CO CO CO CO CO CO CO CO CO

- Figure 2.9.Examples of linear and bent geometry of [H(W(CO)5)2 ]

2.1.8 Liquid Clathrate and Ionic Liquids

Liquid clathrates were first discovered by Atwood in 1969.27 Upon mixing two reagents in toluene, two liquid layers appeared. The top layer consisted of excess toluene and the bottom layer contained the product as well as toluene

(Figure 2.10).20 The layers were completely immiscible (like oil and water). This later became the indication for the presence of a liquid clathrate.27 They found that a liquid clathrate was a cage or layered-like structure that contained anions

with counter ions and aromatic molecules trapped inside.28 The first liquid clathrate they made was from the following reaction (Equation 2.3)27:

+ - KN3 + 2AlMe3 K [N3(AlMe3)2 ] (Equation. 2.3)

The cation and anion became a host for the aromatic guest.27 Further experimentation showed that the shape of the anion was a good indication of the formation the liquid clathrate.27

Figure 2.10: Representation of a liquid clathrate with excess aromatic

An anion with a bent geometry resulted in a liquid clathrate, however, if the anion was linear then a liquid clathrate would not form.27 For a liquid clathrate to form there must be (1) a strong cation-anion attraction (2) a low lattice energy (3) no possibility of association via formation of dimers, trimers etc.28 Non spherical geometry of the anion is the usual cause of low lattice 22

energy. The strong attraction between the cation and anion allows the ions to be further apart and expand thereby allowing the aromatic molecules to fill the layers.28 Therefore favorable interaction sites between the anion to the cation seemed to play an important role in formation of the liquid clathrates, as can be seen in Figure 2.11.27 Figure 2.11 shows the packing of the potassium ion

27 around the azide ion of KN3, K[AlMe3N3], and K[AlMe6N3]. If a dimer, [KN3]2, is able to form then liquid clathrate formation is prevented. With the introduction of crown ethers, dimer formation is prevented and the clathrate forms.27

- - - CH 3 CH3 H3C N Al H C Al Al CH 3 CH N 3 N 3 N CH3 H C CH3 N 3 N N N N

+ - Figure 2.11: The interaction sites ( ) available for the K cation to the N3 anion in KN3, KN3(AlMe3) and KN3(AlMe3)2.As the steric hindrance increases, the K+ cation has fewer possible sites for interaction with the anion.29

Another unique quality of a liquid clathrate is the amount of aromatic held within the host.28 For each liquid clathrate system there is a maximum amount of aromatic that can be absorbed into the liquid clathrate. Once that amount is reached, all additional aromatic solvent will separate on top, forming a second layer.28 A cartoon of how an aromatic solvent might fit within a liquid clathrate, is

shown in Figure 2.12. The amount of aromatic or solvent species depends on a few characteristics of the compounds involved. The larger the anion and cation the bigger the layers become, therefore, more aromatic solvent can be absorbed.

Also, as the size of the aromatic increases, fewer aromatic molecules can fit into

28 any given liquid clathrate. For example K[N3(AlMe3)2] has an aromatic/anion ratio of 5.8 with benzene, but only a ratio of 3.8 with toluene.27 Given the presence of two different aromatics molecules, the host will tend to absorb the smaller aromatic over the larger.30 When only a minimum amount of aromatic is present, the complex is considered to be ―hungry‖ and is in need of more aromatic; this property could be explored for potential applications.27 Although a small percentage of nonaromatics such as hexane can be substituted for the aromatic into the liquid clathrate, solvents such as diethylether, tetrahydrofuran, and dioxane will disrupt the liquid clathrate resulting in an ionic solution.28

Figure 2.12: Two dimensional model of a liquid clathrate adapted from ref. 28 24

Once the basic principle of these liquid clathrates was discovered it was found to apply beyond the area of organoaluminum chemistry,27 such as the liquefaction of coal.27 A liquid clathrate containing toluene in contact with coal turns immediately black and extracts material at room temperature at a faster rate than toluene itself.27 The tendency for liquid clathrates to prefer smaller aromatics over larger ones allows for useful applications in the separation of aromatics.27 The further possibility of extraction is promising because the host generally does not react with the guest, allowing for further application in a variety of areas, including separation of optical isomers with the use of chiral hosts.27

2.1.7 Reactions of metal-silicon compounds with bases

A possible mechanism to explain the formation of

+ - [SiR3(HMPA)1or2 ][H(W(CO)5)2 ] involves the heterolytic cleavage of a metal- silicon bonds by the base HMPA. This section will discuss cleavage of metal- silicon bonds by bases. There are multiple examples of metal-silicon bond in

. + 31 metal carbonyl complexes by bases to give the [SiR3 nBase ] cation. An older review considers the IR spectra of such complexes was done to examine the structure of these complexes in 1982.31 For example, it was observed that the

-1 - complex H3SiCo(CO)4 had carbonyl stretches between 2105 cm and 2025 cm

1,31 . however, the base complex H3SiCo(CO)4 2NMe3 has only one strong band at

-1 - 31 1882 cm , this band is similar to the bands observed for Co(CO)4 . It was, therefore, concluded that the general formula for these systems was (Equation

2.4) when the metal carbonyl anion is a WCA.31 The resulting cation was a base

. + - R3SiMLm + nBase (R3Si nBase) MLm (n = 1 or 2) (Eq. 2.4 ) stabilized siliconium cation with either tetravalent or hypervalent bonding.31 No crystal structures were reported for these early systems. A more recent example of this type of reaction was combination of Fe(CO)4(SiCl3)2 with HMPA. The

+ HMPA stabilized the siliconium cation, [SiCl3(HMPA)3 ], which was identified through IR and NMR studies. Crystals were also isolated that were suitable for

X-ray diffraction (Figure 9)32 This structure was very similar to the structure by

- Denmark (Figure 8). In all the systems described by Equation 2.4, the MLm is a stable transition-metal carbonylate ion.

+ - Figure 2.13. Ball and stick model of [SiCl3(HMPA)3 ] [SiCl3Fe(CO)4 ] from ref. 29 26

2.1.8 General goals

The objective of this research was to improve a general synthesis for siliconium cations through a metal-assisted route. The use of metal carbonyl reagents for the formation of silicon bonds to different bases has been previously established, suggesting this was a reasonable route. These siliconium cations have been proposed as highly reactive intermediates in organic synthesis and therefore are of great interest in optimizing the reaction for organic chemists.

2.2 Experimental

The following experimental section is composed of the general synthesis and characterization of siliconium cations in a liquid clathrate.

2.2.1 General Experimental

All reactions were carried out in an air and oxygen free environment using standard anaerobic techniques.33 The glove box was filled with argon. The irradiation was carried out in a fused silica flask that was dried in an oven ~120 oC overnight then evacuated immediately before the addition of solvent from a solvent purification system, PureSolvTM. The flask was taken into a glove-box where further reagents were added. The quartz flask was attached to an atmosphere of argon in the photolysis box. The photolysis equipment consisted of a 450 watt Havonia medium pressure UV lamp housed in a fused silica cooling jacket. Further reactions were carried out in a dry and oxygen free environment in Pyrex flasks that were dried overnight in an oven ~120 oC. The flasks were either assembled and evacuated immediately or evacuated in the glove-box port and assembled in the glove-box.

2.2.2 Materials

Cr(CO)6 and W(CO)6 were purchased from VWR and were further purified through vacuum sublimation on a Schlenk line. HMPA was purchased from

VWR and was stirred over CaH2 and distilled onto activated 4 Å molecular sieves. The hydrosilanes were purchased from Gelest, dried over activated 4 Å molecular sieves, and distilled over activated 4 Å molecular sieves. The chlorosilanes were treated with CaH2 to remove dissolved HCl. K[B(C6F5)4] was purchased from Boulder Scientific. Benzene and tetrahydrofuran (THF) were purified using the PureSolvTM system. The d6 benzene and d8 THF were purchased from Cambridge Isotopes and dried over and distilled from activated 4

Å molecular sieves at least three times.

2.2.3 Spectroscopy and X-ray crystallography

Routine 1H, 13C and 29Si NMR spectra were obtained on a Varian INOVA

400 MHz or Varian 500 MHz spectrometer using a 5 mm switchable probe at 30 o 1 C. H NMR spectra were referenced to the solvent peak at 7.16 ppm for C6D6.

The 31C NMR spectra were referenced to the solvent peak at 128.93 ppm for

29 C6D6. An external reference of TMS was used for the Si NMR in deuterated benzene (0 ppm). 29Si NMR were collected using a DEPT 45 pulse sequence. In order to eliminate contamination by the components of air, the NMR tubes were flame sealed under vacuum. FT-IR spectra were taken on a Bomen FT-IR spectrophotometer. The IR samples were prepared in a glove-box; placed in a desiccator for brief storage and transferred from the desiccator to the instrument.

The spectra were obtained immediately in order to minimize exposure to oxygen and water. Crystals were studied on a Bruker SMART Apex CCD diffractometer.

In the glove-box crystals were placed on a microscope slide, covered in

Paratone® oil, and placed in a desiccator. The crystals were quickly examined under a microscope in air, transferred to the diffractometer and immediately cooled to ~150 K. Crystal structures were solved by Dr. Matthew J. Panzner and

Brian D. Wright. Mass spectral data was obtained on a SYNAPT HDMSTM Q/ToF

(Water, Beverly MA) instrument. A syringe filled with a solution of the analyte was prepared in the glove-box and transferred to the instrument in an argon filled, o-ring-sealed tube. MS data was obtained by Alyison M. Leigh and

Vincenzo Scionti.

2.2.4 Synthesis of W(CO)5HMPA

W(CO)6 (1.056 g, 3.000 mmol) and HMPA (0.583g, 3.00 mmol) were added to benzene (~ 50 mL) in a fused silica flask. The colorless solution,which was irradiated overnight, resulted in an orange solution. In some cases, section

2.2.5, this solution of W(CO)5HMPA, was used without further purification. The volatile components were removed on a Shlenk line and an orange, partly crystalline solid formed. The product was analyzed by FT-IR to find a mixture of

W(CO)5HMPA and W(CO)4(HMPA)2. The orange crystals were characterized by

34 X-ray crystallography and found to be W(CO)4(HMPA)2. The crystals were removed. The yield of W(CO)5HMPA was ~66%. FT-IR (benzene and THF):

ν(CO, cm-1): 2070 (w), 1980 (vs), 1922 (s).

+ - 2.2.5 Synthesis of [SiR3(HMPA)n ][H(M(CO)5)2 ] (n = 1, 2); R = alkyl, aryl, H; M =

Cr, W

+ - This procedure is for the preparation of [SiEt3(HMPA) ][H(M(CO)5)2 ]. A similar procedure was used for the other silanes. A solution of impure

W(CO)5HMPA (.950 g, 2.00 mmol) and W(CO)4(HMPA)2 in ~ 50 mL of benzene was mixed with SiEt3H (0.233 g, 2.00 mmol) in the glove box. The reaction was lightly stirred for 24 hours to 5 days at room temperature, length of time depended on the individual reaction as well as the temperature of the room. The reaction formed two layers, with the top layer being orange and containing

W(CO)6, W(CO)4(HMPA)2, W(CO)5HMPA and excess HMPA as revealed by

NMR and IR spectroscopy. The bottom layer was a viscous dark orange liquid

+ - that contained [SiEt3(HMPA) ][H(W(CO)5)2 ] and a small amount of starting

+ - materials before purification. The [Si(Et)3HMPA] [HW2(CO)10] liquid clathrate was separated from the top benzene layer by decantation. The resulting dark orange liquid clathrate was washed with about 5 mL benzene to remove any reactants. The new top layer of excess benzene was removed by decantation.

The total number of washings ranged between three and ten until the color of the washings became consistently pale yellow. Often synthesis stopped at the purified liquid clathrate, but the ionic liquid was sometimes obtained through removal of the volatile components on the high-vacuum line. The yield of

+ - + [SiEt3(HMPA) ][H(W(CO)5)2 ] was ~70%. ESI-MS [SiEt3HMPA ] = 294.3 m/z

+ theoretical: 294.2 m/z; [OP(NMe2)3H ] 180.0 m/z theortical: 180.1 m/z;

+ - [OP(NMe2)2 ] = 135.0 m/z theoretical: 135.1 m/z; [HW2(CO)8 ] = 592.8 m/z theoretical: 592.8 m/z; with consecutive losses of carbon monoxide. FT-IR

-1 1 (benzene/THF), ν(CO, cm ): 2041 (m), 1932 (s), 1871 (s); H NMR (C6D6, ppm):

2.20 (d J 1H-31P = 4.2 Hz), 0.741 (t), 0.378 (q), -12.21(s with 183W satellites J 1H-

183 13 13 183 W = 41.9 Hz), C NMR (C6D6, ppm): 202.2 (trans), 200.1(cis) (J C- W),

13 31 31 36.7 (d J C- P = 4.2 Hz), 6.5, 5.5; P NMR (C6D6, ppm): 25.7;

+ - -1 [SiPhH2(HMPA)2 ][H(W(CO)5)2 ]: FT-IR (benzene/THF), ν(CO, cm ): 2041(m),

1 1932 (s), 1871(s); H NMR (C6D6, ppm): 7.40 (m), 7.25 (m), 5.37, 2.01 (d), -

183 1 183 13 11.87(s with W satellites J H- W = ) C NMR (C6D6, ppm): 202.2, 200.1,

31 13 31 134.8, 132.6, 129.5, 128.9, 36.5(d J P- C = 4.7 Hz); P NMR (C6D6, ppm):

29 1 29 27.4; Si NMR (C6D6, ppm): -92.6 (t J H- Si= 283 Hz)

+ - + - 2.2.6 Synthesis of a mixture of [Si(Et)3HMPA] [B(C6F5)4] and K [H(W(CO)5)2 ]

- The [Si(Et)3HMPA][H(M(CO)5)2 ] liquid clathrate prepared as described above was attached to the high vacuum line; the volatiles were removed resulting in a very thick ionic liquid. The ionic liquid was dissolved in about 20 mL of

+ - diethyl ether and a slight excess of K B(C6F5) (1.000 g, 2.000 mmol) was added to the flask and stirred overnight. The volatile components were removed on the high vacuum line and a yellow powder formed. The yellow powder was dissolved

in 10 mL of THF, resulting in an orange solution. About 50 mL of hexane was layered slowly on top of the orange solution and allowed to diffuse through the solution overnight. This reaction resulted in a viscous brown liquid that was possibly a liquid clathrate under a yellow solution. The layers were separated by decantation. The volatile components were removed on the high-vacuum line, during which an orange thick liquid started to form. As the volume diminished, a few crystals formed in the thick liquid, at which time the flask was removed from the vacuum line and placed on the bench top overnight. The following morning more crystals had formed. The crystals were light yellow plates and were separated manually from other needle like crystals, the plate crystals were

+ - identified as [Si(Et3)HMPA ][B(C6F5)4 ]. The needle like crystals were crudely

+ - identified as K [H(W(CO)5)2 ] but the quality of the crystal did not allow for

+ complete solution of the data set. ESI-MS: [SiEt3HMPA ] = 294.2382 m/z

+ theoretical: 294.213 m/z; [OP(NMe2)3H ] = 180.1221m/z theoretical: 180.1266

- m/z; [B(C6F5)4 ] = 678.9272 m/z theoretical: 678.9773 m/z; X-ray data: Table 2.1

Table 2.1: X-ray crystal data of [SiEt3HMPA][B(C6F5)4] and W(CO)4(HMPA)2

Molecular formulas [SiEt3HMPA][B(C6F5)4] W(CO)4(HMPA)2

Empirical formula C36H33BF20N3OPSi C16H36N6O6P2W Formula weight 973.52 654.30 Temperature 100(2) K 273(2) K Wavelength 0.71073 Å 0.71073 Å Crystal system Triclinic Monoclinic Space group P-1 P2(1)/n

Unitcell dimensions a = 10.5130(7) Å a = 8.6248(7) Å b = 13.4013(9) Å b = 20.6694(17) Å c = 14.4258(10) Å c = 15.3663(12) Å α = 84.3050(10)°. = 90° β = 88.2140(10)°. = 96.1580(10)° γ= 81.5810(10)°  = 90° Volume 2000.3(2) Å3 2723.5(4) Å3 Z 2 4 Density (calculated) 1.616 Mg/m3 1.596 Mg/m3 Absorption coefficient 0.228 mm-1 4.397 mm-1 F(000) 984 1304 Crystal size 0.33 x 0.22 x 0.08 mm3 0.23 x 0.14 x 0.12 mm3 Theta range for data collection 1.42 to 25.00°. 1.66 to 26.30°. Index ranges -12<=h<=12, -10<=h<=10, -15<=k<=15, -25<=k<=25, -16<=l<=17 -19<=l<=19 Reflections collected 14613 21109 Independent reflections 7021 [R(int) = 0.0265] 5519 [R(int) = 0.0537] Completeness to theta = 25.00° 99.6 % 99.9 % Absorption correction Semi-empirical from Semi-empirical from equivalents equivalents Max. and min. transmission 0.9820 and 0.9285 0.6205 and 0.4312 Refinement method Full-matrix least-squares Full-matrix least-squares on F2 on F2 Data / restraints / parameters 7021 / 0 / 597 5519 / 0 / 292 Goodness-of-fit on F2 1.016 1.042 Final R indices [I>2sigma(I)] R1 = 0.0381, R1 = 0.0331, wR2 = 0.0767 wR2 = 0.0501 R indices (all data) R1 = 0.0554, R1 = 0.0473, wR2 = 0.0847 wR2 = 0.0568 Largest diff. peak and hole 0.294 and 0.526 and -0.333 e.Å-3 -0.625 e.Å-3

2.3 Results and Discussion

This project was originated over ten years ago in the Tessier laboratories.34 It involved the reaction of group six hexacarbonyl compounds irradiated by a medium pressure Hg lamp in the presence of HMPA in benzene forming a group six pentacarbonyl HMPA species that was then reacted with a silane to produce cationic species of the general formula

+ - [SiR3(HMPA)1or2 ][H(M(CO)5)2 ] (Scheme 2.2). However, the synthesis was not developed well enough and the characterization was incomplete to allow for publication at that time.

h 2 M(CO)6 + 3 HMPA M(CO)5HMPA + M(CO)4(HMPA)2 - CO + - 2 M(CO)5HMPA + SiR3X [SiR3(HMPA)1or2 ][H(M(CO)5)2 ] M = W or Cr X = H or Cl R = allyl or aryl Scheme 2.2. General, two-step synthesis of + - [SiR3(HMPA)1or2 ][H(M(CO)5)2 ]

Therefore, this work had a few major goals, one, improving the synthesis to a practical two-step process, two, obtain complete characterization including mass spectrometry and X-ray crystallography. Step one in the synthesis was not practical because complete isolation of M(CO)5HMPA would oxidize and turn green, even if kept in the box, when all HMPA was removed. In the presence of

excess HMPA and with time M(CO)5HMPA would favor the production of

M(CO)4(HMPA)2 and M(CO)6. In addition, step two of the process forms a liquid product that seems to require a variable amount of time. This liquid product is then very difficult to crystalize, the one crystal structure obtained from previous work had an R value of 9% This work, therefore, developed a simpler synthesis that avoided the need to purify the products of Equation. 2.5.

SiR X h 3 3 M(CO) + 4 HMPA 2 M(CO) HMPA + M(CO) (HMPA) 6 - CO 5 4 2 + - [SiR3(HMPA)1or2 ][H(M(CO)5)2 ]

M = W or Cr (Eq. 2.5) X = H R = allyl or aryl

Another challenge with these reactions has been reproducibility. Two students had attempted these reactions and were not able to get a consistent formation of products. As a result of the work done by Denmark, discussed in

Equation. 2.1, these reactions now have the potential of making a practical system for organic chemists and, therefore, make a greater contribution to the science community than was previously expected.

Difficulty in publishing the original findings in our laboratories was partially because characterization was incomplete. Although characterization by NMR and IR had been substantial, the only crystal structure obtained from these reactions had been a rough data set the products of a redistribution reaction in

+ 2+ 2 [SiPhH (HMPA) ] [SiPhH(HMPA) ] + SiPhH + HMPA Eq. 2.6 2 2 3 3

Equation 2.6, which had not been successfully reproduced. These ionic products formed a liquid clathrate. Part of the reason that liquid clathrates form is due to the fact that the anion and cation cannot form crystalline material and therefore are ionic liquids that form liquid clathrates with aromatic solvent. Therefore, another goal of this work was to confirm the synthesis based on the previous characterization,34 and then find other methods of characterization such as mass spectrometry and isolation of the cations with a different anion for X-ray determination.

2.3.1 Reaction Chemistry

The reaction of a number of silanes, SiR3H, with W(CO)5(HMPA) in

+ - benzene yielded the ionic complexes [SiR3(HMPA)n ][H(W(CO)5)2 ] (n = 1 or 2), as shown in Eq. 2.7. These air-sensitive complexes resulted in liquid clathrates with benzene, and in a few cases, toluene. Below is a comprehensive list of all products made in these laboratories. Consecutive washings with benzene would remove the vast majority of the unreacted starting materials. Further removal of benzene from the clathrate resulted in an ionic liquid. The cationic complexes shown in Eq. 2.7 have one or two molecules of HMPA bound to the silicon atom resulting in either four or five-coordinate silicon. The number of HMPA molecules

bound to the silicon appears to be controlled by a combination of both electronic and steric factors.

C6H6 + - SiR3H + 2M(CO)5(HMPA) {[SiR3(HMPA)n ][H(M(CO)5)2 ]} (Eq. 5)

R3 = PhH2 R3 = (Hex)H2 n = 2 R = Ph H M = W 3 2 R3 = Et3 R3 = Et2H n = 1 R3 = (Hex)3 M = Cr R = PhH n = 2 3 2

The formation of liquid clathrates and ionic liquids made these complexes very difficult to crystalize. In an attempt to crystalize

+ - [SiPhH2(HMPA)2 ][H(W(CO)5)2 ] all of the volatiles were removed from the liquid clathrate and the residue was kept under continuous vacuum for a week.

+ - Crystals of [SiPhH(HMPA)3 ][H(W(CO)5)2 ]2 were isolated along with starting

2+ material (Figure 2.14). The dication, [SiPhH(HMPA)3 ], was formed by the disproportionation reaction shown in Equation 2.6.34 Only few crystals were obtained from this disproportionation reaction. Attempts to reproduce this reaction have been unsuccessful.

+ Figure 2.14. Isotropic drawing of the crystal structure of SiPhH(HMPA)3 (H was not found) from ref 34

+ In an effort to crystalize the [SiEt3(HMPA) ] cation, an ion exchange

+ - reaction was carried out in diethyl ether with K [B(C6F5)4 ]. The diethyl ether was 39

removed and the powder was dissolved in THF and layered with hexane. This resulted in the formation of two layers, the top layer was a yellow/orange liquid, the bottom layer was a thick brown liquid that seemed more viscous than the top layer. The brown layer was presumably a liquid clathrate. After separation, slow removal of the volatile components of the top layer resulted in two sets of crystals that were separated manually. The square plate crystals were

+ - [SiEt3(HMPA) ][B(C6F5)4 ] (Figure 2.15). Smaller needle-like crystals were

+ - K [H(W(CO)5)2 ].

+ - Figure 2.15. Thermal ellipsoid plot of [SiEt3(HMPA) ][B(C6F5)4 ] at a 50% probability

2.3.2 Physical Properties

Liquid clathrate behavior was first described by Atwood as described in Section 2.1.8.29 There are a number of observations that suggest the complexes are liquid clathrates. (1) The formation of two immiscible liquid layers when anions of similar bent geometry are formed in the presence of aromatics.

(2) The removal of small quantities of benzene from the clathrates took hours on a high-vacuum line, suggesting that the benzene was trapped within the liquid

+ - clathrate. (3) The complex [SiPhH2(HMPA)2 ][H(W(CO)5)2 ] reproducibly retained twenty-six moles of benzene per mole of complex before exhibiting the presence

34 - of two liquid layers. There is similar bent structure of [H(W(CO)5)2 ] and the

- - bent [X(AlMe3)2 ] ions. It seems that [H(W(CO)5)2 ] shares the same low ability to

- + coordinate to the siliconium cations as [N3(AlMe3)2 ] had with K (Figure. 2.11)

2.3.3 Spectra Characterization

2.3.3.1 IR

- The anions of general form [H(W(CO)5)2 ] were identified by a combination of NMR and IR techniques. IR spectral data is listed in Table 2.1 as well as literature values. As seen in Table 2.1, the IR bands of the carbonyl ligands of

- 24 [H(M(CO)5)2 ] (M = W or Cr) are similar to those observed in THF. The absorption positions in the carbonyl regions of the IR spectrum were within experimental error of those observed for the benzene liquid clathrates of

- [SiR3(HMPA)n] [H(W(CO)5)2]. There was no evidence for the related [M(CO)5H ] anions by IR or NMR.35

- Table 2.2. IR values for [(M(CO)5)2X , BLC = benzene liquid clathrate

-1 - Cation M X medium  CO (cm ) for [(M(CO)5)2X ref

+ [SiPhH2(HMPA)2 ] W H BLC 2041 w, 1932 vs, 1871 vs this work

2+ [SiPhH(HMPA)3 ] W H BLC 2042 w, 1927 vs, 1871 vs 33

+ [SiPh2H(HMPA)2 ] W H BLC 2041 w, 1926 vs, 1870 vs 33

+ [SiPh2Cl(HMPA)2 ] W H BLC 2041 w, 1927 vs, 1871 vs 33

+ [Si(n-Hex)3(HMPA) ] W H BLC 2041 w, 1926 vs, 1870 vs 33

+ [SiEt2H(HMPA) ] W H BLC 2041 w, 1926 vs, 1870 vs 33

+ [SiEt3(HMPA) ] W H BLC 2041 w, 1926 vs, 1870 vs this work

+ [Si(n-Hex)H2(HMPA)2 ] W H BLC 2041 w, 1926 vs, 1870 vs 33

+ [Na(THF)n ] W H THF 2041 w, 1941 vs, 1879 s 22

+ [NEt4 ] W H THF 2043 w, 1943 vs, 1880 s 22

+ [SiPhH2(HMPA)2 ] Cr H BLC 2029 w, 1935 vs, 1876 vs 33

+ [Na(THF)n ] Cr H THF 2032 m, 1942 vs, 1879 vs 22

+ [NEt4 ] Cr H THF 2033 w, 1943 vs, 1881 s 22

2.3.3.2 Mass Spectrometry

Being that the compounds of interest [SiR3(HMPA)n] [H(W(CO)5)2] are ionic compounds it seemed that mass spectrometry would be an appropriate method of analysis being that mass spectrometry is an analytical method that

only observes charged species. An attempt was initially made to obtain the mass spectrum of the liquid clathrate itself, but the liquid clathrate was too viscous to use in the instrument. Therefore, THF was used to disrupt the liquid clathrate and obtain the spectra.

The mass spectra of [SiR3(HMPA)n] [H(W(CO)5)2] was obtained. In the

+ positive mode, [SiEt3HMPA ] was observed with a m/z of 294.3 with an

+ identifying isotope pattern (Figure 2.16). Protonated HMPA, O=P(NMe2)3H , was observed at 180.0 m/z, and OP(NMe2)2 at 135.0 m/z. In the negative mode, the

- - parent anion [HW2(CO)10 ] was not observed. However, [HW2(CO)8 ] (Figure

2.17) was observed. Consecutive loss of carbonyl ligands with a corresponding

- mass of 28 resulted (Figures 2.18 and 2.19). In [HW2(CO)m ] the anions for m =

8, 7,6, 4, 3 and 2 were observed. In the gas phase, water and THF also coordinated to the tungsten atoms instead of CO. HW2(CO)4THF could be observed with consecutive losses of carbonyl ligands, as well as, HW2(CO)5H2O with consecutive loss of carbonyl ligands in the instrument. This further proves that the anion is water sensitive. The fragmentation of carbonyl ligands from transition metal complexes is a very common occurrence in mass spectrometry.36

+ Figure 2.16. ESI-MS [SiEt3HMPA ], experimental (left) and theoretical (right)

- Figure 2.17. ESI-MS negative mode of [HW2(CO)8 ], experimental (left) theoretical (right)

Figure 2.18. ESI-MS negative mode showing loss of carbonyl ligands (experimental)

Figure 2.19. Theoretical isotopic distribution of compounds of [HW2(CO)6], HW2(CO)4THF, HW2(CO)7 and HW2(CO)8 45

+ - The mass spectrum of [SiEt3(HMPA) ][B(C6F5)4 ] was obtained in a solution of THF in order to avoid the liquid clathrate. In the positive mode the

+ [SiEt3(HMPA) ] was observed at a m/z of 294 (Figure. 2.20). In the negative

- mode the [B(C6F5)4 ] anion was also observed at m/z of 679 (Figure 2.21)

+ Figure 2.20. Mass spectrum of [SiEt3(HMPA) ]. Experimental(left) theoretical(right)

- Figure 2.21. ESI-MS negative mode of [B(C6F5)4 ] experimental (left) theoretical (right)

2.3.3.3 NMR spectroscopy

1 - The H NMR spectra of the [H(W(CO)5)2 ] anion has a very distinctive coupling pattern as a result of the H-W coupling.24 Figure 2.22 shows the highly

8 - negative chemical shift at -12.17 in d THF which is characteristic of [H(W(CO)5)2

183 37, 38 ] showing the W satellites. The JH-W = 41.9 Hz, this agrees with the value given in the literature of 41.9 Hz.24

1H_phenyl2

0.030

0.025 -12.17

0.020

0.015 Normalized Intensity Normalized

0.010

-12.22 -12.13

0.005

-12.09 -12.26

-12.05 -12.10 -12.15 -12.20 -12.25 Chemical Shift (ppm)

Figure 2.22. 1H NMR spectrum of the tungsten-hydride resonance of the - [H(W(CO)5)2 ] anion

In general the 29Si NMR resonances for five coordinate compounds are upfield from four coordinate compounds. The typical range for five coordinate silicon compounds is -170 to -40 ppm compared to four coordinate compounds which have a range of 24 to -76 ppm.39-41 Six coordinate silicon compounds are further upfield, however, the range does overlap with that of the five coordinate species. An upfield shift from the phenyl silane, SiPhH3, to the five-coordinate

+ siliconium cation, SiPhH2(HMPA)2 of 33 ppm occurs resulting in a resonance at -

92.6 ppm. In addition to a resonance shift, an increase in the Si-H coupling constant is also characteristic of an increase in coordination number.39, 40 The

+ SiPhH2(HMPA)2 cation has a coupling constant of 283 Hz, an increase of 84 Hz from the coupling constant of the free silane which was 199 Hz. The formation of five-coordinate siliconium cations in this chemistry seems to be dependent of the sterics. For example, the triethylsilane, SiEt3H produces the four-coordinate

+ siliconium cation, SiEt3HMPA rather than bonding to two HMPA molecules which would create a five-coordinate species.

2.3.4 X-ray crystal structures

Yellow crystals of W(CO)4(HMPA)2 were isolated from the reaction of

HMPA and W(CO)6 irradiated in benzene. The crystal structure was obtained at

273 K to avoid cracking of the crystal. Selected bond distances and angles are listed in Table 2.3 and a thermal ellipsoid diagram is shown in Figure 2.24. The

HMPA ligands are cis to each other on the roughly octahedrally coordinated

tungsten center. The O-W-O angle at 76.64(11)o is surprisingly small due to the large steric nature of the HMPA ligands compared to the carbonyl ligands. The

P-O bond distances are 1.487(3) Å and 1.481(3) Å these are slightly longer than the P-O bond length in HMPA, 1.477(1) Å.42

Figure 2.23. Thermal ellipsoid plot of W(CO)4(HMPA)2 at 50% probability

o Table 2.3 Selected bond distances (Å) and angles ( ) of W(CO)4(HMPA)2 W(1)-C(14) 1.917(5) W(1)-C(13) 2.023(5) W(1)-C(15) 1.923(5) P(1)-O(1) 1.487(3) W(1)-C(16) 2.019(5) P(2)-O(2) 1.481(3 W(1)-O(2) 2.202(3) W(1)-O(1) 2.203(3) C(14)-W(1)-C(15) 87.3(2) C(14)-W(1)-C(13) 85.4(2) C(14)-W(1)-C(16) 87.0(2) C(15)-W(1)-O(2) 97.23(16) C(15)-W(1)-C(16) 85.83(19) C(16)-W(1)-O(2) 93.23(16) C(13)-W(1)-O(2) 94.74(16) C(13)-W(1)-O(1) 90.18(15) C(14)-W(1)-O(1) 98.83(16) O(2)-W(1)-O(1) 76.64(11 C(16)-W(1)-O(1) 95.87(16)

+ - The crystal structure of [SiEt3(HMPA) ][B(C6F5)4 ] was obtained at 100 K.

+ - The unit cell consists of the cation [SiEt3HMPA ] and the anion [B(C6F5)4 ] (Figure

2.24). The anion and cation are well separated with the closest Si-F distance of

4.878 Å, beyond the range of any significant interaction. The geometry at silicon is roughly tetrahedral (Figure. 2.25) with deviations probably due to thermal motion in one of the ethyl groups. The bond angles around silicon are relatively close to 109.50 (Table 2.4). A typical silicon-carbon (sp3) bond distance is 1.860

Å (s.d. 0.02 Å).43 The silicon-carbon bond lengths are, therefore, within the range of normal silicon-carbon single bond distances. The average silicon-oxygen bond length for a tetracoordinate silicon atom bound to a dicoordinate oxygen atom is 1.629 Å (s.d 0.03 Å).43 The silicon-oxygen bond in this complex is

1.7070(16) Å, this distance is slightly longer than a typical silicon-oxygen distance; this is probably due to the dative nature of the HMPA ligand rather than a normal covalent bond. The bond angle for the P(1)-O(1)-Si(1) in this complex is 144.11(11)o, which is within the average value for a Si-O-X bond angle of

135.4o (s.d. 15.8o).43 In a search of the Cambridge Structural Database of silicon-HMPA compounds it was observed that the Si-O-P bond angle is highly varied from 142.86o – 177.27o indicating that the angle at oxygen has little do to with the energy of the complex. However, this bond angle is slightly smaller than those HMPA complexes that are five and six coordinate but similar to other four coordinate compounds.

+ - Figure 2.24. Thermal ellipsoid plot of [SiEt3(HMPA) ][B(C6F5)4 ] with 50% probability

o + Table 2.4. Selected Bond Distances (Å) and Bond Angles ( ) for [SiEt3(HMPA) ] Si(1)-O(1) 1.7070(16) Si(1)-C(5B) 1.843(10) Si(1)-C(2) 1.846(3) Si(1)-C(3) 1.854(3) P(1)-O(1) 1.5428(15) O(1)-Si(1)-C(2) 107.54(10) O(1)-Si(1)-C(3) 107.79(10) O(1)-Si(1)-C(5A) 101.59(19) O(1)-Si(1)-C(5B) 106.5(3) C(2)-Si(1)-C(5A) 122.1(2) C(2)-Si(1)-C(5B) 100.7(4) C(3)-Si(1)-C(5A) 106.5(2) C(3)-Si(1)-C(5B) 123.0(4) C(2)-Si(1)-C(3) 110.26(12) P(1)-O(1)-Si(1) 144.11(11) 51

+ Figure 2.25. Thermal Ellipsoid plot of [SiEt3(HMPA) ] at 50% probability

+ - In the silyl cation [SiEt3 ][B(C6F5) ] the closest interaction was 4.04 Å between silicon and fluorine.44 The silyl cation did have distant coordination from a toluene molecule that allowed the silicon to be nearly planar at the sp2 silicon with the closest interaction of a carbon from the toluene molecule being 2.18 Å.44.

This work now indicates that the base stabilization of HMPA increases the coordination number of silicon to four, and that the anion has even less

+ - interaction in [SiEt3(HMPA) ][B(C6F5)4 ]. The bond length between silicon and oxygen are slightly shorter than the bond distances observed in SiCl4(HMPA)2

+ 22 (1.770 Å) and SiCl3(HMPA)3 (1.766 Å – 1.778 Å) observed in Denmark’s work. 52

This elongation is probably due to steric effects of the octahedral silicon versus the tetrahedral silicon.

Needle-like twin crystals were also obtained from the anion exchange

+ - reaction flask. They were crudely identified as K [H(W(CO)5)2 ], however, the quality of the crystals did not allow for complete solution of the data set. At the time of this dissertation efforts to recrystallize this product had been unsuccessful.

2.4 Conclusion:

Interest in siliconium cations has been growing in recent years due to their role as intermediates in a number of organic reactions. This work has shown convincing evidence of a synthesis for the creation of siliconium cations from silicon hydrides using a metal assisted route. This synthesis is carried out under mild conditions and with relatively inexpensive reagents. The siliconium cations seem to be relatively stable for a long time when kept under an argon atmosphere. This stability could be of great use in the study of proposed cationic intermediates in some organic reactions, (equation. 1) specifically in the allyation of aldehydes where HMPA like bases are used as initiators.

Furthermore, a new class of liquid clathrates has been discovered that confirms the previous thoughts of a particular anion shape required for such

- complexes to form. This anion, [H(M(CO)5)2 ], has been shown to be a valuable weakly coordinating anion that is synthesized in a two-step process with

inexpensive reagents. The affordability of this synthesis is in vast contrast to

- other weakly coordinating anions such as carboranes or the [B(Ar)4 ] anions, and therefore further increases the potential usefulness of these systems.

CHAPTER III

Reactions of Chlorophosphazenes with HMPA

3.1 Introduction

This research is focused around the reactions of HMPA with chlorophosphazenes. Phosphazenes and their importance will be discussed in

Section 3.1.1. The purpose of studying the reaction of the chlorophosphazenes

[PCl2N]3 or [PCl2N]4 with HMPA was to better understand the cationic intermediates in the ring opening polymerization (ROP) to give [PCl2N]n. The

ROP will be described in Section 3.1.2. Claims of phosphorus cations have been made in the literature with Lewis acids and in the presence of Lewis bases; these will be discussed in Section 3.13. The reaction of chlorophosphazenes with

HMPA leads to an oxygen transfer rather than the desired cation. The resulting

- anion, [P3N3Cl5O ], is similar to the parent compound in the hydrolysis of chlorophosphazenes; this anion will be discussed in Section 3.1.4. The counter

+ ion in this reaction is the P(NMe2)3Cl cation; examples of this cation in the literature will be discussed in Section 3.1.5. The overall bonding of [PCl2N]3 and

[PCl2N]4 will be discussed in Section 3.1.6. 55

3.1.1 Introduction to phosphazenes

Phosphazenes have a basic structure of alternating phosphorus-nitrogen atoms. These compounds have two substituents on each phosphorus atom, and no substituents on the nitrogen atoms. Phosphazenes comprise a wide variety of compounds, not only because of various substituents but also because of their differing structures. Figure 3.1 shows a few examples of the most widely studied chlorophosphazenes.45 The substituent, R, on the phosphorus atom can be a halogen, pseudohalogen, amino, azido or a variety of organic groups such as alkyl, aryl, alkoxy and alkylamino, to name a few. When the R group is chlorine the compounds are known as chlorophosphazenes. By altering the R group different phosphazenes can have tailored properties, which has led to vast areas of application.

R R R R R P N P R P R R N N N N N P R R P P R P N P R n R N R (n ~ 15,000) R R

[PR2N]3 [PR2N]4 [PR2N]n

R = halide, OR, NHR, alkyl, or aryl Figure 3.1 Examples of common phosphazenes

Understanding the chlorophosphazenes is vital to advancement of phosphazenes in general because the majority of phosphazenes are synthesized from chlorophosphazenes. There is great potential for polyphosphazenes to become used in industry more than siloxanes, currently the most widely used inorganic backbone polymer. In fact, there are four start-up companies based on polyphosphazenes.46-49 They can be used as biomaterials, elastomers and flame retardants, to name a few applications, however, despite the potentially limitless application of these polymers they are not yet used in industry to any great extent. This is due to the low yield and expense of these compounds.

In general, if the substituents are OR groups, the polymer is flexible and very stable to heat and harsh chemicals. This leads to applications as elastomers,

50 foams, batteries, coatings and fire-proofing. If the substituents are NR2, the polymers are water degradable and therefore potentially useful as coatings for time-released drugs and as a matrix for bone repair.50 The developments of these diverse polymeric materials had spurred a continued interest in the chemistry of phosphazenes, especially in the last two decades. Commercial interest in the use of phosphazenes in the areas of aerospace, communications, and medical sensors will continue to drive this area of research for years to come.50

There are a variety of synthetic routes to the chlorophosphazene polymers

(Scheme 3.1). The traditional route is the ring opening polymerization of [PCl2N]3

o 45 at ~250 C. In practice, [PCl2N]4 is usually also present during the ROP, though

it polymerizes more slowly. The ROP uses cheap reagents, but the reproducibility is not always consistent. Other routes involve more expensive reagents and have poorer yields or produce shorter polymer. Therefore, the full potential of polyphosphazenes has never been fully realized, largely because of synthetic challenges.

[PCl2N]3 ROP at rt + melt "SiEt3 " ROP ~214 oC [PCl2N]3 + [PCl2N]4 NH Cl + PCl [PCl2N]n -HCl 4 5 ~250 oC Cl BCl Condensations 3 -X-Z ~210 oC Cl

Cl Cl X P N Z

Cl Scheme 3.1. Synthetic routes of the chlorophosphazene polymer

A major method of forming the chloropolymer, [PCl2N]n, is through ring opening polymerization of the chlorophosphazene trimer and tetramer.45, 51 The first known synthesis of phosphazenes was in 1834. The reaction of phosphorus pentachloride with ammonia resulted in the major product of (NPNH)n as well as

45 a small amount of [PCl2N]3. In the late 1890’s, Stokes indicated that the small

50 chlorophosphazene molecules had cyclic structures. He also heated [PCl2N]3 and caused polymerization. He called this product, which was completely insoluble in all solvents, ―inorganic rubber‖.50 In 1924, Schenk and Romer

developed an improved synthesis for the small molecule chlorophosphazenes

(Eq. 3.1).45 During the 1950’s, the direct synthesis of

solvent PCl5 + NH4Cl [PCl2N]m + 4 HCl (3.1) 120 oC m =3 - 12 organophosphazenes was first studied. The first mechanistic studies of the ROP were done in 1960.45, 50, 52 It was then realized that the ―inorganic rubber‖ that was observed by Stokes was a cross-linked polymer. The mechanism of the

ROP for [PCl2N]3 and [PCl2N]4 to give [PCl2N]n is not completely understood.

Therefore, the study of possible intermediates can lead to a greater understanding of the process and allow for increased yield of products

3.1.2 Proposed intermediates of the ring-opening polymerization

There are a few proposed mechanisms for the ROP, the most popular was proposed by Allcock (Scheme 3.2).51 The first step of the Allcock’s mechanism is the heterolytic cleavage of one of the phosphorus-chloride bonds to give a phosphazenium cation. This cationic mechanism is supported by several

o observations, typical melt polymerization of [PCl2N]3 occurs between 230-250 C.

o Below 210 C molten [PCl2N]3 has low conductance but as the temperature is increased the conductivity of the molten solution also increases sharply.3 This suggests an ionic mechanism. Also, the use of radical initiators has very little

3 effect on the rate of polymerization. The most useful catalysts, like BCl3, have

been reagents that would be expected to remove a chloride ion from the

3 phosphorus. The temperature required for the ROP increases from [PBr2N]3 to

[PCl2N]3 to [PF2N]3 this also indicates that the energy needed to dissociate the phosphorus-halide bond is involved in the rate determining step of the polymerization.

Cl Cl N Cl Cl P P N Cl P Cl heat Cl P Cl N N N N P o ~250 C P Cl Cl [PCl2N]3 Cl Cl

phosphazenium cation Cl N Cl P Cl P Cl N N P Cl Cl Cl Cl N N Cl P P Cl Cl P P P Cl Cl N N Cl P N P N N N Cl N P Cl Cl Cl Cl P Cl Cl Cl Cl

phosphonium cation

Scheme 3.2. Allcock’s proposed cationic ring opening polymerization mechanism for the conversion of [PCl2N]3 to [PCl2N]n

The initial step of the mechanism is the formation of a phosphazenium cation that is then stabilized by the nitrogen of another molecule of trimer forming a phosphonium cation.50 Our goal was to stabilize a proposed intermediate of the ROP with the base HMPA (Figure 3.2). This phosphonium cation could then

help gain some insight into the mechanism of the ROP, thereby leading to improved synthesis of the polymer.

Me2N NMe2 P NMe2 Cl O P N N Cl- Cl P P Cl N Cl Cl Figure 3.2. HMPA stabilized phosphonium cation

3.1.3 Phosphorus cations

There have been examples of cationic phosphorus nitrogen compounds in the literature. Some of these examples involve phosphorus (III) such as RN≡P+-

53 + 54 L2, RN≡P -L. However, given that the chemistry of our research is with phosphorus (V), only those compounds will be emphasized here.

There were claims of phosphazenium cations in older literature. It was suggested that [PCl2N]3 could undergo a Friedel-Crafts type reaction due to its presumed similarity to benzene. It was suggested that aluminum chloride, AlCl3, in the presence of [PCl2N]3 would remove a chloride and form a phosphazenium

45 cation and AlCl4 (Equation 3.2). Similar claims were made for BCl3, SbCl5 and

55,56,57 TaCl5. However, some of these have been disproven by Tessier and

Cl Cl Cl P P N N N N + AlCl [AlCl4 ] (Eq. 3.2) Cl Cl 3 Cl P P P P Cl Cl N Cl Cl N Cl

coworkers.58,59 It is now obvious that when water is vigorously eliminated from the reaction of AlCl3 or GaCl3 and [PCl2N]3 adduct formation occurs rather than

59 formation of a phosphazenium cation (Figure 3.3). SbCl5 has also been shown to give protonated adducts with [PCl2N]3 (Figure 3.3), even with rigorous elimination of water. The source of the proton is presumed to be from water imbedded in the reaction glassware.58 This shows that the previous claims of a phosphazenium cation with AlCl3, and other Lewis acids, were misleading because of the presence of water.

Cl Cl Cl Cl Cl Cl

P AlCl3 P GaCl3 P H N N N N N N Cl Cl Cl Cl Cl P P P P P P Cl Cl N Cl Cl N Cl N Cl Cl

Figure 3.3. Adduct formation from the reaction of [PCl2N]3 with AlCl3, GaCl3 and SbCl5

Ian Manners has synthesized a base stabilized cation that may be viewed as an intermediate in the condensation reaction to form polychlorophosphazenes.60 Manner’s initial attempt was to form

+ - [Cl2P=NSiMe3 ][OTf ] by reacting Cl3P=NSiMe3 with silver triflate, Ag[OTf]. 62

60 However the reaction produced [PCl2N]n and SiMe3OTf. Therefore, the use of a base was thought to stabilize the cation. The reaction of 4-(dimethylamino)- pyridine (DMAP) with Cl3P=NSiMe3 and Ag[OTf], resulted in the complex

. 60 [DMAP PCl2=NSiMe3]OTf. The Ag[OTf] acted as a chloride abstractor and immediately formed the precipitate, AgCl. When the reaction was performed without Ag[OTf] the same cation was formed with a chloride anion. However, this complex was in equilibrium with the starting materials.60 It is interesting to note that the only way to stabilize the proposed intermediate was with the use of a basic ligand. An attempt was then made to stabilize the phosphorus cation with a phosphine base, such as, PPh3 and P(nBu)3. However, when PR3 was

60 combined with Cl3P=NSiMe3, PCl3 and R3P=NSiMe3 were the products.

Therefore, although the nitrogen base, DMAP, was successfully used to form a base stabilized cation, a phosphine base results in a transfer reaction between the two phosphorus centers.

Manner’s later discovered that a phosphine base could be used to stabilize a phosphoranimine cation when chlorines were not used in the

61 reaction. For example when BrMe2P=NSiMe3 was reacted with PMe3 the general reaction in Equation 3.3 was observed.61 The reaction was successful with a number of different phosphines. Manners also attempted to

R' - BrR'2P=NSiMe3 + PR''3 R''3P P N SiMe3 Br (Eq 3.3) R'

+ remove the phosphine group from the cation to isolate R’2P=NSiMe3 by using a

Lewis acid. However, when the phosphine was removed with B(C6F5)3, the original bromine reactant formed. The free cation was also not observed when the triflate anion was used.61

The only phosphonium cation from chlorophosphazenes that has been

+2 - . 62 characterized by X-ray crystallography is [P(DMAP)2N ]3[Cl ]6 19CHCl3. This hexacation was synthesized under very harsh conditions. [PCl2N]3 and six equivalents of DMAP, 4-dimethylaminopyridine, were microwaved in superheated chloroform (100 oC).62 The crystals isolated from this reaction are highly sensitive and decomposed when removed from the mother liquor. The P-N bond lengths in this compound on average are 1.561 Å.62 This P-N bond length is on the short end of normal bond lengths in the phosphazene ring.3 The bond lengths were symmetrical which is typically seen with symmetric substitution of ligands.3 This hexacation has been the closest compound to the phosphonium cations proposed in the ROP of [PCl2N]3 (Scheme 3.2).

Another example of ligand transfer between two phosphorus centers, as

53 was seen in Manner’s work, is proposed for the reaction of DMAP with POCl3.

+ - 53 In SO2 solution, which produced POCl3, SOCl2 and [(DMAP)2PO2 ]Cl . The author, Cernik, proposes the mechanism shown in Scheme 3.3 based on species observed in the 31P spectrum.53 He suggests that the first step in the mechanism is the formation of a phosphonium cation with simultaneous heterolytic cleavage of a phosphorus-chloride bond. Additional POCl3 reacts with the phosphonium

cation forming an oxygen- and chlorine- bridging cation. The cation then undergoes nucleophilic attack by a chloride forming PCl5 and (DMAP)PO2Cl.

+ - DMAP then displaces the chloride of (DMAP)PO2Cl forming [(DMAP)2PO2 ] Cl ,

31 which was the only final product isolated. The PCl5 was not detected in the P

NMR presumably because of further reaction with SO2, regenerating POCl3 and

SOCl2.

POCl3 + SOCl2 DMAP + POCl3

+ + SO2 Cl DMAP + POCl Cl + - 3 - [(DMAP)POCl2 ]Cl Cl P P O Cl PCl5 + (DMAP)PO2Cl O Cl Cl + DMAP

+ - [(DMAP)2PO2 ]Cl

+ - Scheme 3.3 Proposed mechanism of [(DMAP)2PO2 ] Cl in SO2 by the reaction of DMAP and POCl3

This work proposes a possible mechanism of an oxygen-chloride ligand transfer between two phosphorus centers. This reaction chemistry has not been thoroughly studied, and has potential to be a new area of reactions to explore.

- 3.1.4 The P3N3Cl5O anion

- 63 The first mention of the [P3N3Cl5O ] anion is from 1981. Di Gregorio was attempting to use the [PCl2N]3 as a reagent to convert carboxylic acids to

anhydrides through the reaction in Equation 3.5. These products were characterized by 1H and 31P NMR, IR and elemental analysis.63

[PCl2N]3 + 2 RCOOHNR3' (RCO)2O + R3'N HCl + (Eq. 3.5) R 'NH+ P N Cl O- 3 3 3 5

Oxygenated products were also seen when [PCl2N]3 and [PCl2N]4 were combined with dimethylsulfoxide, DMSO.64 The DMSO was not dried prior to use. The general reactions are shown in equations 3.6 and 3.7.64 The final

[PCl2N]3 + 6 DMSO [PO(OH)NH]3 CH2ClSCH3 + 5 CH2ClSCH3 ( Eq. 3.6)

[PCl2N]4 + 8 DMSO [PO(OH)NH]4 CH2ClSCH3 + 7 CH2ClSCH3 ( Eq. 3.7)

products as well as some intermediates were analyzed by mass spectrometry.64

Due to these studies, the pathway in Scheme 3.4 was proposed.64 This pathway shows that the first step of this process is the formation of a phosphazenium cation, similar to the proposed first step intermediate of the ROP.50 This reaction

64 pathway was assumed to be similar for [PCl2N]4 as well. Notice that the source of the oxygen seems to come from a transfer reaction of the oxygen from DMSO

64 and the source of the chloride is from [PCl2N]3.

+ - N3P3Cl6 + DMSO [N3P3Cl5DMSO ]Cl N3P3(OH)Cl5 + ClCH3SCH3

N3P3(OH)Cl5 + 2 DMSO N3P3(OH)3Cl3 3ClCH2SCH3

DMSO

N H P O (OH) 6ClCH SCH 3 3 3 3 3 2 3

Scheme 3.4 Proposed reaction pathway of [PCl2N]3 with DMSO

Perhaps the obvious way to form this anion would be as a product of the hydrolysis of [PCl2N]3. It has long been established that water plays an important role in the polymerization of the cyclic chlorophosphazenes.45 Rigorous avoidance of water during the ROP results in a much longer reaction time than if trace amounts of water are introduced.3 However, if too much water is introduced to the reaction an insoluble cross-linked polymer forms.3 Therefore it was established that trace impurities of water can be essential, yet inhibitory in large quantities. The most advantageous amount of water has never been quantified. One possible advantage to the presence of water in the polymerization is that at high temperatures the water helps to cleave a phosphorus-chloride bond forming a hydrolyzed trimer species shown in

Equation 3.8.3

Cl Cl Cl N Cl N + H O P P Cl P P 2 Cl O Cl ( Eq. 3.8) N N - HCl N N H P P Cl Cl Cl Cl 67

A study of the hydrolysis products was completed by monitoring the 31P

NMR spectrum of the [PCl2N]3 with one equivalent of water over the period of two days.65 A number of monomeric species were identified in the reaction, as shown

65 in Scheme 3.5 for the hydrolysis of [PCl2N]3. It should be noted that the initial hydrolysis product could be drawn as either of its tautomers as shown in Figure

3.5.

H Cl Cl Cl Cl Cl N Cl N N P P P P O H O O P P O Cl H2O Cl 2 Cl N N N N - HCl N N H - HCl H P P P Cl Cl Cl Cl Cl Cl

H O - HCl H2O - HCl 2

H Cl OH N Cl OH P P O H O N Cl 2 O P P O N N - HCl H N N P H P Cl Cl Cl Cl

65 Scheme 3.5. Proposed hydrolysis of [PCl2N]3 with DMSO

Cl Cl Cl Cl N N P P Cl P P O Cl O H N N N N H P P Cl Cl Cl Cl

Figure 3.4. Tautomers of P3N3Cl5OH

- The [P3N3Cl5O ] was also isolated, somewhat unexpectedly, in the Tessier

59 laboratories. In an attempt to prove presence of protonic impurities in [PCl2N]3,

59 the super base, (t-Bu)N=P(N(CH2)4)3, was added to [PCl2N]3. The products of this reaction, in ~5% yield, were [(t-Bu)NH-P(N(CH2)4)3)][P3N3Cl5O] (Equation.

3.9).59 This complex presumably formed through deprotonation of a hydroxyl group on the trimer formed though a reaction of [PCl2N]3 with adventitious water.59

HO N Cl N(t-Bu) Cl P P Cl + N P N N N N P Cl Cl or its tautomer

H N(t-Bu) O N Cl N P N Cl P P Cl ( Eq. 3.9) N N N P Cl Cl

+ 3.1.5. The P(NMe2)3Cl cation

There are a few examples of the synthesis of this phosphonium chloride in the literature. The oldest example is the reaction shown in Equation. 3.10.66

HMPA + POCl [P(Me N) Cl+] [O PCl -] 3 2 3 2 2 (Eq. 3.10) 69

The most used application of the phosphazenium chloride is as a catalyst supplying chloride ions to organic acids under mild conditions that could not be obtained using thionyl chloride.67 In this example the phosphazenium chloride is made from HMPA and phosgene, COCl2, and then tethered to silica gel to act as a catalyst in a silica column (Scheme 3.5) .67 Another example of the formation

Cl N P N Cl- MeO N MeO Si Bu MeO N N MeO Si MeO N P N H -HCl MeO Bu N - - Cl or HCl2 Silica

Si O OH HDMS O N O N O Si N P N O Si N P N O Bu N O Bu N

- - - - Cl or HCl2 Cl or HCl 2 + Scheme 3.5. The tethering reaction of [P(NMe2)3Cl ] to silica gel

+ 68 of (Me2N)3PCl was through a reaction of (Me2N)3P and Cl-I. The goal of this synthesis was to form complexes analogous to (Me2N)3PI2, however, through

+ 68 crystallization in methylene chloride the (Me2N)3PCl cation formed.

3.1.6 Bonding of phosphazenes

Although the study of phosphazenes has been extensive, the nature of the unsaturated P-N bond is still debated. The P-N bond is generally short (1.58 Å) relative to saturated phosphazanes (1.77 Å) with the shortest bond lengths observed when the substituents are highly electronegative.69 This short bond length would tend to imply multiple bond character; this is also supported by the lack of bond length alternation in the cyclic phosphazenes.69 The most common early bonding model was established by Dewar; this model stated that delocalization occurred through dP-pN overlap resulting in ―islands‖ of electron density over the P-N-P units.70 However, it has now been accepted that the d character in hypervalent main group elements is minimal.13 It was then suggested by Reed and Schleyer that the multiple-bond character was due to negative hyperconjugation.71 They concluded that compounds with the general formula, X3AY (F3NO, O3ClF, etc.), contained highly ionic σ bonds with AY binding classified as negative hyperconjugation.72 With hyperconjugation the electron density at nitrogen can be donated into the P-N * or P-Cl * orbital thereby allowing the phosphorus and nitrogen to be closer and have more covalent character. These findings led to a study of the electronic structure of phosphazenes by Chaplin.69 Chaplin’s study confirmed that negative hyperconjugation plays a significant role in the P-N bond of phosphazenes, about

69 18% in [PCl2N]3. Ionic bonding appears to the dominant feature due to the substantial charge transfer between the phosphorus and nitrogen confirming

ionic character to the P-N bond.69 Figure 3.5 shows the zwitterion model and the more traditional drawing. Although the zwitterion model is more accurate, the most common representation of [PCl2N]3 is one showing multiple bonds.

However, if the multiple bonds are seen as one sigma interaction and a general interaction involving ionic bonding and hyper conjugation then this model can be used successfully. It was also observed that substituted cyclotriphosphazenes have variations in bond length due to destabilization of the σ*PN+PX orbital, further supporting the importance of negative hyperconjugation.69 There was also evidence of weak cyclic delocalization due to the multiple-bond character derived from negative hyperconjugation, fulfilling some of the criteria for aromaticity, making cyclotriphosphazenes potential candidates for ―inorganic benzene‖.69 In general the most important finding of this study was that the chemical binding in phosphazenes is not dominated by d-orbital participation, but by ionic bonding and negative hyperconjugation.69

Cl Cl Cl Cl Cl Cl P P P N N N N N N Cl Cl Cl Cl Cl Cl P P P P P P Cl N Cl Cl N Cl Cl N Cl

Figure 3.5. Multiple bond drawing of [PCl2N]3 (left) zwitterion model of

[PCl2N]3 (right)

3.1.7 General goals

Due to the general interest in polyphosphazenes there is a great desire to understand the ring-opening polymerization of [PCl2N]3. One suggested mechanism involves the formation of a phosphonium cation. The general goal of this project was to isolate an HMPA stabilized phosphonium cation in an effort to better understand the chemistry of the chlorophosphazenes.

3.2 Experimental

This following experimental section is composed of the general reaction of chlorophosphazenes with HMPA

3.2.1 General Experimental

All reactions were carried out in an air and oxygen free environment using standard anaerobic techniques.33 The glove box was filled with argon. The vacuum line had an ultimate capability of 10-4 mmHg. Reactions were carried out in a dry and oxygen free environment in Pyrex flasks that were dried overnight in an oven ~120 oC. The flasks were either assembled and evacuated immediately or evacuated in to the glove-box port and assembled in the glove-box. UV irradiation was carried out in a fused silica flask, that was dried in an oven overnight and evacuated immediately before the addition of solvent from the

PureSolvTM solvent purification system. The flask was taken into a glove-box where other reagents were added. The fused silica flask was attached to an atmosphere of argon in the photolysis box. The photolysis equipment consisted of a 450 watt Havonia medium pressure UV lamp housed in a fused silica cooling jacket.

3.2.2 Materials

[PCl2N]3 was purchased from Aldrich (99.99) and was further purified by sublimation. [PCl2N]4 was donated by Prof. Christopher Allen of the University of

Vermont. HMPA was purchased from VWR and was stirred over CaH2 and distilled from and stored over activated 4 Å molecular sieves. The mixture of rings, [PCl2N]m (m = 5 – 12) was synthesized by David Bowers. K[B(C6F5)4] was purchased from Boulder Scientific. Cr(CO)6 and W(CO)6 were purchased from

VWR and were further purified through sublimation on a Schlenk line. Benzene and tetrahydrofuran (THF) were purified using the PureSolvTM system. The d6 benzene was purchased from Cambridge Isotopes, dried over activated 4 Å molecular sieves, and distilled three times onto freshly activated 4 Å molecular sieves.

3.2.3 Spectroscopy and X-ray crystallography

Routine 1H, 13C and 31P NMR spectra were obtained on a Varian INOVA

400 MHz or Varian 500 MHz spectrometer at 30 oC in a 5 mm switchable probe.

1 The H NMR spectra were referenced to the solvent peak at 7.16 ppm for C6D6.

31 The C spectra were referenced to the solvent peak at 128.39 ppm for C6D6.

31 External references were for the P spectra, a capillary tube of 85% H3PO4 in a

5 mm NMR tube of deuterated benzene (0 ppm) was used. In order to eliminate oxygen contamination, the NMR tubes were flame sealed under vacuum.

Crystals were studied on a Bruker SMART Apex CCD diffractometer. In the glove-box crystals were placed on a microscope slide, covered in Paratone® oil, and placed in a desiccator. The crystals were quickly examined under a microscope in air, transferred to the diffractometer and immediately cooled to

~150 K. Crystal structures were solved by Dr. Matthew J. Panzner. Mass 75

spectral data was obtained on a SYNAPT HDMSTM Q/ToF (Water, Beverly MA) instrument. A syringe filled with a solution of the analyte was prepared in the glove-box and transferred to the instrument in an argon filled, o-ring sealed tube.

ESI-MS data was obtained by Vincenzo Scionti. EPR spectra was obtained on an ELEXSYS E-500. Fused silica EPR tubes were prepared in a glove box and were sealed with a Teflon® and o-ring Solv-Seal joint. EPR data was obtained by Dr. Joseph Massey.

3.2.4 Reaction of M(CO)5HMPA with [PCl2N]3 M = Cr or W

M(CO)5HMPA was synthesized using the same method outlined in the previous chapter (section 2.2.4). [PCl2N]3 ( .752 g, 1.50 mmol) was added to a solution of M(CO)5HMPA in toluene in the glove box. Two layers formed, which suggested the presence of a liquid clathrate. M = Cr: FT-IR(benzene and THF), v(CO, cm-1): 2063, 2034, 1957, 1908, 1850; 31P NMR (d8 THF, ppm): 55.779 (s),

19.840 (s), 27.169 (broad), 13.417 (broad), -6.613 (s), -14.661(broad) EPR: g =

1.97 M = W: g⸗ = 1.93, g┴ = 1.76

+ - 3.2.5 Synthesis of [P(NMe2)3Cl ][P3N3Cl5O ]

[PCl2N]3 ( 0.251 g, 0.500 mmol) and HMPA ( 0.093 g, 0.500 mmol) were added to benzene (~30 mL) in a 100 mL flask resulting in a colorless solution.

The contents were stirred for ~30 min. at room temperature. The volatile

components were removed on a vacuum line resulting in white, crystalline material. Yield = ~70%. In some cases reactions were carried out in an NMR tube with .0348 g, 0.100 mmol of [PCl2N]3 and 0.017 g, 0.100 mmol of HMPA.

31P NMR (d6 benzene, ppm): 53.43 (s), 24.09 (s), 19.50 (d), -6.60 (t); 1H NMR (d6 benzene, ppm ): 2.47 (d); 13C(d6 benzene, ppm) 37.486 (d) ESI-MS (THF, m/z):

+ - [P(NMe2)3Cl ]: 198.1018 m/z theoretical: 198.0927; [P3N3Cl5O ]: 327.8026, theoretical: 327.7667.

+ - 3.2.6 Synthesis of [P(NMe2)3Cl ][P4N4Cl7O ]

[PCl2N]4 (.231 g, 0.500 mmol) and HMPA (0.093 g, 0.50 mmol) were added to benzene (~30 mL) in a 100 mL flask resulting in a colorless solution.

The contents were stirred for ~45 min. The volatile components were removed on a vacuum line resulting in white, crystalline material. Yield = ~70% In some cases reactions were carried out in an NMR tube with .0464 g,100 mmol of

31 6 [PCl2N]4 and 0.017 g, 0.100 mmol of HMPA. P (d benzene, ppm): 53.95 (s),

23.81 (s), -6.36 (s), -6.96 (t), -16.11 (d of d), -21.38 (t); 1H (d6 benzene, ppm):

13 6 + 2.55 (d); C (d benzene, ppm): 37.59 (d) MS ( THF, m/z): [P(NMe2)3Cl ]:

- 198.1070 m/z theoretical: 198.0927; [P4N4Cl4O ]: 440.7486 m/z, theoretical:440.6842;

3.2.7 Reaction of [PCl2N]n (n = 5-12) with HMPA

[PCl2N]n (0.153 g) and a large excess of HMPA was combined in benzene

(~30 mL). The reaction was stirred for ~45 min. The volatiles components were removed on the high-vacuum line resulting in crystalline white precipitate. 31P

NMR (d6 benzene, ppm): 53.43 (s), 23.73 (s), -6.65 (t), -17.03 (d), -17.19 (d), -

17.74 (dd), -17.87 (dd), -18.26 (d), -18.98 (s), -21.88 (t).

+ - + - + - Table 3.1. X-ray crystal structure data of [P(NMe2)3Cl ][P3N3Cl5O ], [P(NMe2)3Cl ][P4N4Cl7O ]. [P(NMe2)3Cl ][B(C6F5)4 ] + - and [P(NMe2)3Cl ]Cl + - + - + - + - Compound [P(NMe2)3Cl ][P3N3Cl5O ] [P(NMe2)3Cl ][P4N4Cl7O ] [P(NMe2)3Cl ][B(C6F5)4 ] [P(NMe2)3Cl ]Cl Empirical formula C6H18Cl6N6OP4 C6H18Cl8N7OP5 C30H18BClF20N3P C6H18Cl2N3P Formula weight 526.84 642.72 877.70 234.10 Temperature 100(2) K 100(2) K 100(2) K 100(2) K Wavelength 0.71073 Å 0.71073 Å 0.71073 Å 0.71073 Å Crystal system Monoclinic Monoclinic Triclinic Monoclinic Space group P2(1)/c P2(1)/c P-1 P2(1)/n a = 8.392(2) Å a = 10.818(3) Å a = 8.0635(8) Å a = 8.008(3) Å b = 21.563(6) Å b = 10.114(3) Å b = 19.9748(19) Å b = 10.588(5) Å c = 12.185(3) Å c = 22.474(7) Å c = 20.647(2) Å c = 14.175(6) Å Unit cell dimensions α = 90° α= 90° α= 93.366(2)° = 90° β = 107.462(4)° β= 99.408(6)° β= 97.962(2)° = 92.623(6)° γ = 90° γ = 90° γ = 93.253(2)°  = 90° Volume 2103.4(9) Å3 2425.8(13) Å3 3280.6(6) Å3 1200.7(9) Å3 79 Z 4 4 4 4 Density (calculated) 1.664 Mg/m3 1.760 Mg/m3 1.777 Mg/m3 1.295 Mg/m3 Absorption -1 -1 -1 -1 coefficient 1.129 mm 1.274 mm 0.310 mm 0.635 mm F(000) 1064 1288 1744 496 Crystal size 0.22 x 0.11 x 0.10 mm3 0.15 x 0.06 x 0.05 mm3 0.32 x 0.17 x 0.15 mm3 0.19 x 0.13 x 0.04 mm3 Theta range for data 1.89 to 26.30° 1.84 to 26.30° 1.02 to 26.30° 2.40 to 26.29°. collection -10<=h<=10, -13<=h<=13, -10<=h<=10, -9<=h<=9, Index ranges -26<=k<=26, -12<=k<=12, -24<=k<=24, -12<=k<=13, -15<=l<=15 -27<=l<=27 -25<=l<=25 -17<=l<=17 Reflections collected 16632 18855 26581 9206 Independent 4259 [R(int) = 0.0392] 4930 [R(int) = 0.0610] 13164 [R(int) = 0.0314] 2429 [R(int) = 0.0669] reflections Completeness to 99.8 % 100.0 % 99.1 % 100.0 % theta = 26.30° Absorption Semi-empirical from Semi-empirical from Semi-empirical from Semi-empirical from correction equivalents equivalents equivalents equivalents

Max. and min. 0.8954 and 0.7892 0.9391 and 0.8319 0.9550 and 0.9074 0.9751 and 0.8889 transmission Full-matrix least-squares on Full-matrix least-squares on Full-matrix least-squares on Full-matrix least-squares Refinement method F2 F2 F2 on F2 Data / restraints / 4259 / 0 / 310 4930 / 0 / 270 13164 / 0 / 1021 2429 / 0 / 115 parameters Goodness-of-fit on 1.063 1.029 1.086 1.052 F2 Final R indices R1 = 0.0440, R1 = 0.0545, R1 = 0.0427, R1 = 0.0506, [I>2sigma(I)] wR2 = 0.1070 wR2 = 0.1183 wR2 = 0.1071 wR2 = 0.1265 R1 = 0.0555, R1 = 0.0780, R1 = 0.0613, R1 = 0.0647, R indices (all data) wR2 = 0.1147 wR2 = 0.1289 wR2 = 0.1130 wR2 = 0.1387 Largest diff. peak 0.938 and 0.638 and -0.565 e.Å-3 1.217 and -0.744 e.Å-3 0.414 and -0.434 e.Å-3 and hole -0.367 e.Å-3

3.3 Results and Discussion

The initial goal of the work was to stabilize a phosphonium cation that is a proposed intermediate of the ring opening polymerization of [PCl2N]3. The first attempts were to use the metal assisted synthesis, outlined in the previous chapter on siliconium cations. After encountering radical species with the metal assisted route a more direct route was attempted. It was soon discovered that although the phosphonium cation was a probable intermediate it was not the final product. Instead the HMPA seemed to exchange its oxygen with a chloride on the phosphazene resulting in an oxygenated species (Equation 3.11). The generality of this reaction with chlorophosphazenes will be discussed in Section

3.3.2

+ - [PCl2N]m + O=P(NMe2)3 [P(NMe2)3Cl ][(PCl2N)m-1(PClON) ] (Equation 3.11)

3.3.1 Metal Assisted Reaction

Using the template of the metal assisted route described in Scheme 2.1, the first experiment involved the reaction of [PCl2N]3 with a solution of

W(CO)5HMPA in benzene. The reaction separated into two layers presumably forming a liquid clathrate and suggesting that the reaction had proceeded as expected as shown in Equation 3.12. Confirmation of the anion was obtained

Cl N Cl HMPA Cl N P P P P Cl Cl + W(CO)5HMPA Cl Cl Cl N N W(CO) Equation 3.12 N N (CO)5W 5 P P Cl Cl Cl Cl through the IR spectra with bands at 2063, 2034, 1957, 1908, and 1850 cm-1.

The confirmation of this anion was significant because it had previously been described in the literature as not stable. However, confirmation that the cation in

Equation 3.12 had been synthesized was not obtained. As was seen in the previous project, isolation of crystalline material was unsuccessful because of the liquid nature of the products. The 31P NMR spectrum was obtained to characterize the cation, however, it did not confirm the presence of the phosphonium cation and showed some broadening of peaks suggesting the possibility of a radical species or exchange phenomenon. Similar observations were seen in reactions of Cr(CO)5HMPA and [PCl2N]3. The EPR spectra were obtained at 4 K for both reactions. The EPR spectra proved the presence of a radical species. By comparison with the literature, the radical species was

73 identified as W(CO)5Cl. A radical species was also observed in the

Cr(CO)5HMPA reaction. Through comparison of literature values, the species

+ 74 producing this EPR signal was Cr(CO)6 . Although these results were interesting it did not give a good indication of what was happening with the chlorophosphazene.

1.0E+07

5.0E+06

0.0E+00

-5.0E+06

-1.0E+07

-1.5E+07

Figure 3.6. EPR spectrum taken at 4.2 K of the radical product (g⸗ = 1.93, g┴ = 1.76), W(CO)5Cl) from the reaction in Equation 3.12 in benzene

1.3E+07

8.0E+06

3.0E+06

-2.0E+06

-7.0E+06

-1.2E+07

-1.7E+07

Figure 3.7. EPR spectrum taken at 4.2 K of the radical product (g = 1.97), + Cr(CO)6 ) of the reaction of [PCl2N]3 and Cr(CO)5HMPA in benzene In order to crystallize the anion or the cation of the liquid clathrate, an anion exchange reaction with K[B(C6F5)4] was conducted in THF. The crystals 83

+ - isolated from that reaction were [P(NMe2)3Cl ][B(C6F5)4 ] (Figure 3.8). This cation will be encountered later in this chapter and at that point, this crystal will be discussed.

This cation suggested that an oxygen/chlorine transfer had occurred between the oxygen of the HMPA and a chlorine of [PCl2N]3. The presence of this cation confirmed the singlet seen in the 31P NMR. The presence of radical species prompted the exploration of a reaction without presence of a metal.

+ - Figure 3.8. Thermal ellipsoid plot of [P(NMe2)3Cl ][B(C6F5)4 ] at 50% probability

3.3.2 Reaction Chemistry of Direct Route

The direct reaction of HMPA with [PCl2N]3, [PCl2N]4 and [PCl2N]m (m = 5-

+ 12) was studied. With each reaction the [P(NMe2)3Cl ] cation was synthesized instead of the anticipated phosphonium cation. A proposed mechanism is shown in Scheme 3.6 for [PCl2N]3. A similar mechanism is expected for the other chlorophosphazenes as well. The phosphonium cation of interest is suspected to

Me2N NMe2 P NMe2 Cl- O Cl N O Cl N Cl Cl N P P Cl P P HMPA P P Cl Cl Cl Cl P Cl Cl N N Me N NMe2 N N 2 NMe N N P 2 P P Cl Cl Cl Cl Cl Cl

Me2N NMe2 P NMe2 Cl O Cl N P P Cl Cl N N P

Cl Cl

Scheme 3.6. Proposed mechanism for the reaction of [PCl2N]3 and HMPA

initially form; however, it could not be isolated. Each of the reactions proceeded very quickly at room temperature, within two hours. The reaction went to completion with an average yield of 70% with a 1:1 ratio of chlorophosphazene to

HMPA. The same reaction was seen with a 1:2 ratio of reagents but it was faster. With the 1:2 ratio of reagents, [PCl2N]3 was completely consumed but the other [PCl2N]m still were present. When the ratio was increased to 1:3, then

+ - further reaction took place resulting in crystalline [P(NMe2)3 ]Cl in all three cases. With a large excess of HMPA the reaction would turn into an insoluble solid over the period of a week or more. The insoluble product has not yet been characterized. In general, the reaction of HMPA with [PCl2N]3 was faster than the reaction with [PCl2N]4. Interestingly, the ROP of [PCl2N]3 is faster than that of

50 [PCl2N]4.

3.3.3 Characterization

The products of the reactions of HMPA with [PCl2N]m (m = 3-12) were characterized by NMR, MS, and X-ray crystallography.

3.3.3.1 NMR

31 The P spectrum from the reaction of [PCl2N]3 with HMPA is shown in

Figure 3.9. Also shown in Figure 3.9 is a scheme that identifies the different

+ phosphorus atoms. The resonance at 53.4 ppm corresponds to the [P(NMe2)3 ] cation. The doublet resonance at 19.5 ppm corresponds to the two equivalent

phosphorus atoms (c and d) coupled, JP-P = 35 Hz, to the phosphorus (b) with an oxygen. The triplet at -6.6 ppm corresponds to the phosphorus (b) with an oxygen coupled, it is coupled to the two phosphorus atoms (b and c), JP-P = 35

Hz. The resonance at 24.1 corresponds to the excess HMPA still present. A

1 13 resonance for the [PCl2N]3 is not present based on the NMR. The H and C

NMR both exhibited a downfield shift from the resonance with HMPA, no other signals were present.

31 6 Figure 3.9. P spectrum of the reaction of [PCl2N]3 with HMPA in d benzene after 1 h. The different phosphorus atoms are identified by letters.

31 The P spectrum of the reaction of [PCl2N]4 with HMPA is shown in

Figure 3.10. Also shown in Figure 3.10 is a scheme that identifies the different

+ phosphorus atoms. The resonance at 53.6 ppm corresponds to [P(NMe2)3 ].

The resonance at -6.6 ppm is unreacted [PCl2N]4. An expansion of the spectrum

- is shown in Figure 3.11, showing the resonances for the [P4N4Cl7O ] anion. The triplet at -7.8 ppm corresponds to the oxygenated phosphorus (b). It is coupled to two phosphorus atoms (two c’s), JP-P = 26 Hz. The doublet of doublets at

-17.2 ppm corresponds to the two phosphorus atoms (c). They are coupled first to the oxygenated phosphorus atom (b) , JP-P = 26 Hz, and the other phosphorus atom (d), JP-P = 22 Hz. The final triplet at -22.0 ppm corresponds to the phosphorus atom (d). It is coupled to the two phosphorus atoms (c), JP-P = 22

Hz. The 1H and 13C NMR both exhibited a downfield shift from the resonance with HMPA, no other signals were present.

31 6 Figure 3.10. P spectrum of the reaction of [PCl2N]4 with HMPA in d benzene after 4 h. The different phosphorus atoms are identified by letters.

Figure 3.11 Expansion region from -7.5 ppm to .22.8 ppm of the 31P - spectrum in Fig. 3.10 showing resonances of the [P4N4Cl7O ] anion. The different phosphorus atoms are identified by letters. 89

31 The P NMR spectrum of the reaction of a mixture of rings [PCl2N]m, m =

5-12, with a large excess of HMPA is shown in Figure 3.12. The value of m was determined through mass spectrometry. The resonances at 53.4 ppm and 53.3

+ ppm correspond to the [P(NMe2)3Cl ] cation but with different anions. The resonance 23.7 ppm corresponds to the large excess of HMPA. An expansion of the anion region of the spectra is shown in Figure 3.13. The resonances upfield show a number of different anions present. The triplet at -6.7 is in the same region of as the oxygenated phosphorus atoms seen in the [PCl2N]3 and [PCl2N]4 reactions. However the coupling constant, J = 35 Hz., does not correspond to any of the other coupling constants. There are clearly multiple anions present although they could not be identified. The larger chlorophosphazene rings are difficult to separate and therefore HMPA could not be reacted with each individual ring.

31 Figure 3.12. P spectrum of the reaction of [PCl2N]m with excess HMPA in d6 benzene after 4h.

Figure 3.13 Expansion of the 31P spectrum in Fig 3.12 showing resonances of the phosphazene anions.

+ The resonance of the [P(NMe2)3 ] cation is in the same general region for every reaction, however, each has a slightly different resonance. This trend has

+ 75 been seen with the Cl4P cation with different anions. Therefore, it is reasonable to assume that the reaction of [PCl2N]m and HMPA resulted in the formation of at least two anions.

3.3.3.2 Mass Spectrometry

+ - [P(NMe2)3Cl ][P3N3Cl5O ] was characterized by ESI-MS. THF was used as a solvent in the mass spectrometer because the benzene did not allow for

+ very good ionization. In the positive mode, peaks for the [P(NMe2)3Cl ] cation at m/z = 198.1018 were observed as shown in Figure 3.14. Protonated HMPA was also observed in the positive mode at m/z = 181.1369, as well as the HMPA

+ - fragment O=P(NMe2)2 at m/z = 135.0791. The [P3N3Cl5O ] anion was observed

- in the negative mode as shown in Figure 3.15. The [[P3N3Cl5 ] anion was also present in the gas phase.

+ Figure 3.14. Positive mode ESI-MS of [P(NMe2)3Cl ] in + - [P(NMe2)3Cl ][P3N3Cl5O ] experimental (left) and theoretical (right)

- Figure 3.15. Negative mode ESI-MS of [P3N3Cl5O ] in + - [P(NMe2)3Cl ][P3N3Cl5O ] experimental (left) and theoretical (right)

+ - [P(NMe2)3Cl ][P4N4Cl7O ] was characterized by ESI-MS using THF as a

+ solvent. The [P(NMe2)3Cl ] cation was observed in the positive mode as is shown in Figure 3.16. Protonated HMPA was also observed in the positive

+ - mode, as well as the HMPA fragment O=P(NMe2)2 . [P4N4Cl7O ] was observed in the negative mode as shown in Figure 3.17. The reactant [PCl2N]4, as the anion, was also present in the negative mode, further suggesting that the

- [PCl2N]4 reaction is a slower reaction. The [P4N4Cl7 ] anion was also present in

- - the negative mode. Therefore, for both [P3N3Cl5O ] and [P4N4Cl7O ], surprisingly facile loss of oxygen atoms is observed in the gas phase.

+ Figure 3.16. Positive mode ESI-MS of [P(NMe2)3Cl ] cation in + - [P(NMe2)3Cl ][P4N4Cl7O ] experimental (left) and theoretical (right)

- Figure 3.17. Negative mode ESI-MS of [P4N4Cl7O ] anion in + - [P(NMe2)3Cl ][P4N4Cl7O ] experimental (left) and theoretical (right)

3.3.3.3 X-ray Crystal Structures

The reaction in Equation 3.13 produced crystals suitable for X-ray

+ - diffraction. The unit cell of [P(NMe2)3Cl ][P3N3Cl5O ] is shown in Figure 3.18

Cl N Cl O O Cl Cl N Cl P P Cl P P P P Cl (Eq. 3.13) N N NMe Me N NMe Cl P Me2N 2 2 2 N N NMe NMe P Cl 2 2 Cl Cl Cl HMPA

The crystals were obtained by crystallizing the reaction mixture. Table 3.2 lists selected bond angles and bond lengths. The crystal structure consists of well-

+ - separated [P(NMe2)3Cl ] cations and [P3N3Cl5O ] anions.

+ - The anion of [P(NMe2)3Cl ][P3N3Cl5O ] will be described first. In

- [P3N3Cl5O ], the P-N bonds adjacent to the P-O bond, P1-N3 and P1-N1 are

76 significantly elongated from the average length observed in [PCl2N]3 at 1.581 Å and are in the range of single bonds. Some shortening of the P-N bonds between N1-P2 and N3-P3 was observed implying an increased bond order between those bonds not adjacent to the P-O bond. This can be seen more clearly in the thermal ellipsoid plot below (Figure 3.19). The phosphorus-oxygen bond is within the range of a double bond. Therefore, a pentavalent phosphorus such as P1 could only have single bonds to its other three substituents, as is observed for its bonds to the N1 and N3 nitrogen atoms. This would suggest that the negative charge of the anion is delocalized among the rest of the phosphorus-nitrogen bonds which is also inferred by the bond shortening between those atoms. The average phosphorus-chlorine bond in [PCl2N]3 is

76 - 1.995 Å. The phosphorus-chlorine bond lengths in the [P3N3Cl5O ] anion are all elongated from those seen in the [PCl2N]3 (Figure 3.19). Because of thermal 95

- motion of two of the chlorine atoms of [P3N3Cl5O ], further meaningful comparisons in P-Cl distances are not possible.

Figure 3.18. Thermal ellipsoid plot of the crystal structure of + - [P(NMe2)3 ][P3N3Cl5O ] at 50% probability

Table 3.2. Selection of bond lengths (Å) and bond angles (o) for + - [P(NMe2)3Cl ][P3N3Cl5O ] Cl(6A)-P(4A) 2.013(4) P(2)-N(2) 1.591(3) P(4A)-N(5A) 1.604(5) P(3)-N(3) 1.551(3) P(4A)-N(6A) 1.604(5) P(3)-N(2) 1.585(3) P(4A)-N(4) 1.663(3) Cl(1)-P(1) 2.0777(11) P(1)-O(1) 1.464(2) Cl(2)-P(2) 2.0181(10) P(1)-N(3) 1.617(2) Cl(3A)-P(2) 2.117(5) P(1)-N(1) 1.622(2) Cl(4A)-P(3) 2.110(4) P(2)-N(1) 1.554(2) Cl(5)-P(3) 2.0190(11) N(3)-P(1)-N(1) 111.97(12) P(2)-N(1)-P(1) 121.61(14) N(1)-P(2)-N(2) 120.52(13) P(3)-N(2)-P(2) 117.98(15) N(3)-P(3)-N(2) 120.06(13) P(3)-N(3)-P(1) 122.20(14)

- Figure 3.19. Thermal ellipsoid plot of [P3N3Cl5O ] from the unit cell of + - [P(NMe2)3Cl ][P3N3Cl5O ] with a 50% probability

Products from the reaction is Equation 3.14 were crystalline and suitable

+ - for X-ray diffraction. The unit cell of [P(NMe2)3Cl ][P4N4Cl7O ] is shown in

Cl Cl O N Cl Cl P P Cl N O Cl Cl P P Cl N N P P (Eq. 3.14) NMe N N Me N NMe2 Me2N 2 Cl P P Cl 2 N NMe2 NMe2 Cl P P Cl Cl Cl N Cl Cl HMPA

Figure 3.20. The phosphorus-nitrogen bonds adjacent to the phosphorous- oxygen bond (P1-N1 and P1-N4) again show a lengthening from the average P-

N bond in chlorophosphazenes (1.581 Å).76 The rest of the phosphorus-nitrogen bonds are shorter than the average P-N bond with the exception of the P4-N3A bond. This N3 nitrogen, however, has a large degree of thermal motion and it is therefore difficult to identify the actual length of its bonds. The P1-O1 bond length is again standard for a phosphorus-oxygen double bond with [PCl2N]4.

The P1 phosphorus seems to have single, σ-bonds to the N1 and N4 nitrogens.

Therefore, it is reasonable to assume that the overall negative charge of the anion is delocalized thoughout the other phosphorus nitrogen bonds, similar to

- [P3N3Cl5O ]. In general, all of the P-Cl bonds are elongated from the from the P-

77 Cl bonds in [PCl2N]4.

Figure 3.20. Thermal ellipsoid plot of the crystal structure of - - [P(NMe2)3Cl ][P4N4Cl7O ]

Table 3.3 Selected bond lengths (Å) and bond angles (o) of + - [P(NMe2)3Cl ][P4N4Cl7O ] P(1)-O(1) 1.469(3) P(4)-N(3A) 1.638(19) P(1)-N(1) 1.611(4) Cl(1)-P(1) 2.0495(16) P(1)-N(4) 1.615(4) Cl(2)-P(2) 2.0149(17) P(2)-N(1) 1.543(4) Cl(3)-P(2) 2.0187(17) P(2)-N(2) 1.568(4) Cl(4)-P(3) 1.9830(19) P(3)-N(3A) 1.549(9) Cl(5)-P(3) 2.008(2) P(3)-N(2) 1.566(4) Cl(6A)-P(4) 2.105(13) P(4)-N(4) 1.536(4) Cl(7)-P(4) 2.0189(18) N(1)-P(1)-N(4) 112.24(19) P(2)-N(1)-P(1) 134.1(2) N(1)-P(2)-N(2) 124.1(2) P(3)-N(2)-P(2) 133.9(3) N(3A)-P(3)-N(2) 123.4(4) P(3)-N(3A)-P(4) 127.2(12) N(3B)-P(4)-N(4) 121.3(13) P(4)-N(4)-P(1) 130.3(2)

- Figure 3.21. Thermal ellipsoid plot of the [P4N4Cl7O ] anion from the crystal + - structure of [P(NMe2)3Cl ][P4N4Cl7O ] 99

Figure 3.22 shows the thermal ellipsoid plot of the two cations for the

- - [P4N4Cl7O ] and [P3N3Cl5O ] anions. The phosphorus-chlorine bond distances are statistically the same for the two cations (Table 3.4). The phosphorus- nitrogen bonds are also statistically the same with the exception of the P4A-N4

+ - bond length in the [P(NMe2)3Cl ][P3N3Cl5O ] compound. The apparent elongation of the P4A-N4 bond is most likely observed because of disorder in the NMe2 group of the N4 nitrogen.

+ Figure 3.22. Thermal ellipsoid plots of the [P(NMe2)3Cl ] cations from the + - crystal structures of [P(NMe2)3Cl ][P4N4Cl7O ] (left) and + - [P(NMe2)3Cl ][P3N3Cl5O ] (right) at 50% probability. The NMe2 group at N4 in the latter is disordered.

100

+ Table 3.4. Selected bond lengths (Å) for [P(NMe2)3Cl ] + - + - [P(NMe2)3Cl ][P4N4Cl7O ] [P(NMe2)3Cl ] [P3N3Cl5O ] Cl(8)-P(5) 2.0094(16) Cl(6A)-P(4A) 2.013(4) P(5)-N(5) 1.603(4) P(4A)-N(5A) 1.604(5) P(5)-N(7) 1.604(4) P(4A)-N(6A) 1.604(5) P(5)-N(6) 1.605(4) P(4A)-N(4) 1.663(3)

In an effort to understand the oxygen/chlorine transfer that happens in these reactions it is useful to look at the bond lengths of the reactants compared to the products. The phosphorus-oxygen bond length in HMPA is 1.477(1) Å.42

- - The phosphorus-oxygen bond in the [P3N3Cl5O ] and [P4N4Cl7O ] anions are

1.464(2) Å and 1.469(3) Å respectively. Both of these phosphorus-oxygen bonds formed in these anions are stronger than the phosphorus oxygen bond in HMPA.

+ The phosphorus-chlorine bonds formed in the production of the [P(NMe2)3Cl ] cations are 2.0094(16) Å and 2.013(4) Å in length. The average bond length of a phosphorus-chlorine bond in the [PCl2N]3 is 1.995(5), these bonds are statistically very close.76 The similar length of these bonds implies that the driving force of this reaction is the formation of the stronger phosphorus-oxygen bond in the phosphazene anions. In addition, comparison of all four crystal structures with this cation show that the two cation with an oxygenated phosphazene anion are statistically identical, whereas, the same cations with a

- chloride anion or [B(C6F5)4 ] anion result in slightly longer P-Cl bonds of

2.0568(14) Å and 2.0317(9) Å respectively. This difference could be due to packing forces or a cation-anion interaction. This indicates a general similarity in

+ the interaction of the [P(NMe2)3 ] cation with the oxoanions. 101

3.3.4 Conclusions

The goal of this project was to synthesize phosphonium cations of

[PCl2N]m. Although this was not successful through the metal-assisted route, or the direct route an interesting reaction resulted. It is now known that the reaction of [PCl2N]m with HMPA results in an oxygen/chlorine

+ transfer to give the [P(NMe2)3Cl ] cation and oxygenated anions. This reaction is very similar to early claims in the literature that an oxygen/chlorine transfer occurred between [PCl2N]3 and DMSO. The DMSO work had very limited characterization. This work has been well characterized by NMR, MS and

X-ray crystallography, therefore, significantly advancing the field.

102

CHAPTER IV

Conclusion

4.1 General Conclusions

In general the metal assisted route of forming siliconium cations stabilized by HMPA was successful. The synthesis was optimized by finding that the products of the first step of the synthesis did not need to be isolated, making the process more appealing for application to organic synthesis. Further characterization of these compounds was also obtained through mass spectrometry and X-ray diffraction, in addition to NMR and IR. The tendency for the reaction products to form liquid clathrates made the crystallizing process very difficult, however, crystals suitable for X-ray diffraction were obtain through an ion exchange reaction with K[B(C6F5)4].

The goal of stabilizing phosphonium cations of the chlorophosphazene rings was not successful, although the phosphonium cations are suspected of being an intermediate. Unexpected phosphonium chloride cations were formed

103

through a transfer reaction of the oxygen from HMPA and a chlorine from the phosphazenes. This reaction has some similarity to previous transfer reactions seen in phosphorus chemistry, none of which has been studied in great detail.

This reaction also produced an oxo-chlorophosphazene anion that is suspected of being involved in the hydrolysis of phosphazenes.

Overall the use of a group six metal carbonyl HMPA complex to transfer the base to the phosphorus or silicon atoms was only partially successful. It seems that reaction is favorable when the displaced halide was a hydride rather than a chloride, which when displaced seems to produce radical species.

104

References

(1) Olah, G. A.; Laali, K. K.; Wang, Q.; Prakash, S. G. K. In Siliconium ions; Onium Ions; John Wiley and Sons, Inc.: New York, 1998; Vol. 1, pp 391-424.

(2) Denmark, S. E.; Su, X.; Nishigaichi, Y.; Coe, D. M.; Wong, K.; Winter, S. B. D.; Choi, J. Y. Synthesis of phosphoramides for the Lewis base-catalyzed allylation and aldol addition reactions. J. Org. Chem. 1999, 64, 1958-1967.

(3) Allcock, H. R. Recent advances in phosphazene (phosphonitrilic) chemistry. Chem. Rev. 1972, 72, 315-356.

(4) Spek, A. L.; Terheijden, J.; Kraaykamp, J. G.; Timmer, K. Structure of dioxo[2-(salicylidenamino)phenolato(2-)- O,N,O'][tris(dimethylamino)phosphine oxide]tungsten(VI). Acta Crystallogr. , Sect. C: Cryst. Struct. Commun. 1990, C46, 693-695.

(5) Voronkov, M. G.; Trofimova, O. M.; Bolgova, Y. I.; Chernov, N. F. Hypervalent silicon-containing organosilicon derivatives of nitrogen heterocycles. Russ. Chem. Rev. 2007, 76, 825-845.

(6) Rendler, S.; Oestreich, M. Hypervalent silicon as a reactive site in selective bond-forming processes. Synthesis 2005, 1727-1747.

(7) Miessler, G. L.; Tarr, D. A. Inorganic Chemistry, Second Edition. 1999, 640.

(8) Lambert, J. B.; Kania, L.; Zhang, S. Modern Approaches to Silylium Cations in Condensed Phase. Chem. Rev. (Washington, D. C. ) 1995, 95, 1191-1201.

105

(9) Kim, K.; Reed, C. A.; Elliott, D. W.; Mueller, L. J.; Tham, F.; Lin, L.; Lambert, J. B. Crystallographic evidence for a free silylium ion. Science (Washington, DC, U. S. ) 2002, 297, 825-827.

(10) Arshadi, M.; Johnels, D.; Edlund, U.; Ottosson, C.; Cremer, D. Solvated Silylium Cations: Structure Determination by NMR Spectroscopy and the NMR/Ab Initio/IGLO Method. J. Am. Chem. Soc. 1996, 118, 5120-5131.

(11) Olsson, L.; Ottosson, C.; Cremer, D. Properties of R3SiX Compounds and R3Si+ Ions: Do Silylium Ions Exist in Solution?. J. Am. Chem. Soc. 1995, 117, 7460-7479.

(12) Lambert, J. B.; Zhang, S.; Ciro, S. M. Silyl Cations in the Solid and in Solution. Organometallics 1994, 13, 2430-2443.

(13) Häser, M. Characterization of Electronic Structure in Molecules by One-

Center Expansion Techniques. No Three-Center Four-Electron Bond in PF5. J. Am. Chem. Soc. 1996, 118, 7311-7325.

(14) Short, J. D.; Attenoux, S.; Berrisford, D. J. Additive effects on ligand activated allylation of aldehydes by allyltrichlorosilane. Tetrahedron Lett. 1997, 38, 2351-2354.

(15) Short, J. D.; Attenoux, S.; Berrisford, D. J. Additive effects on ligand activated allylation of aldehydes by allyltrichlorosilane. Tetrahedron Lett. 1997, 38, 2351-2354.

(16) Denmark, S. E.; Winter, S. B. D.; Su, X.; Wong, K. Chemistry of Trichlorosilyl Enolates. 1. New Reagents for Catalytic, Asymmetric Aldol Additions. J. Am. Chem. Soc. 1996, 118, 7404-7405.

(17) Wang, Z.; Wang, D.; Sui, X. Asymmetric allylation of aldehydes with allyltrichlorosilane via a chiral pentacoordinate silicate. Chem. Commun. (Cambridge) 1996, 2261-2262.

(18) Kobayashi, S.; Nishio, K. Facile and highly stereoselective allylation of aldehydes using allyltrichlorosilanes in DMF. Tetrahedron Lett. 1993, 34, 3453-3456.

106

(19) Denmark, S. E.; Fu, J.; Coe, D. M.; Su, X.; Pratt, N. E.; Griedel, B. D. Chiral phosphoramide-catalyzed enantioselective addition of allylic trichlorosilanes to aldehydes. Preparative and mechanistic studies with monodentate phosphorus-based amides. J Org Chem 2006, 71, 1513-1522.

(20) Denmark, S. E.; Coe, D. M.; Pratt, N. E.; Griedel, B. D. Asymmetric Allylation of Aldehydes with Chiral Lewis Bases. J. Org. Chem. 1994, 59, 6161-6163.

(21) Denmark, S. E.; Beutner, G. L. Lewis base catalysis in organic synthesis. Angew Chem Int Ed Engl 2008, 47, 1560-1638.

(22) Denmark, S. E.; Eklov, B. M. Neutral and Cationic Phosphoramide Adducts of Silicon Tetrachloride: Synthesis and Characterization of Their Solution and Solid-State Structures. Chemistry - A European Journal 2008, 14, 234-239.

(23) Hart, D. W.; Bau, R.; Koetzle, T. F. A neutron diffraction study of [Ph4P]+[HW2(CO)10]-. Organometallics 1985, 4, 1590-1594.

(24) Hayter, R. G. Hydrogen bridge bonding in the [M2H(CO)10]- anions (M = Cr, Mo, W). J. Am. Chem. Soc. 1966, 88, 4376-4382.

(25) Bau, R.; Drabnis, M. H. Structures of transition metal hydrides determined by neutron diffraction. Inorg. Chim. Acta 1997, 259, 27-50.

(26) Volpe, M.; Bombieri, G.; Clemente, D. A.; Foresti, E.; Grillone, M. D. Synthesis and physico-chemical characterization of a new series of hydroxide ion acetylacetonate lanthanide(III)-ditungsten decacarbonyl hydride complexes. J. Alloys Compd. 2004, 374, 382-386.

(27) Atwood, J. L.; Davies, J. E. D.; MacNichol, D. D.; Editors Inclusion Compounds, Vol. 1: Structural Aspects of Inclusion Compounds Formed by Inorganic and Organometallic Host Lattices. 1984, 420.

(28) Atwood, J. L. In In Anionic and cationic organoaluminum compounds. Section Title: Organometallic and Organometalloidal Compounds; 1993; , pp 197-132.

107

(29) Steed, J. W.; Atwood, J. L. In Liquid Clathrates; Steed, J. W., Atwood, J. L., Eds.; Supramolecular Chemistry; John Wiley and Sons, Ltd.: West Sussex, United Kingdom, 2009; Vol. 2, pp 854-859.

(30) Robinson, G. H. Structural survey of the organoaluminum coordination chemistry of oxygen and sulfur (thia) crown ethers. Coord. Chem. Rev. 1992, 112, 227-245.

(31) Emeleus, H. J.; Sharpe, A. G.; Editors Advances in Inorganic Chemistry and Radiochemistry, Vol. 25. 1982, 355.

(32) Du, V. A.; Baumann, S. O.; Stipicic, G. N.; Schubert, U. Cleavage of an iron- silicon bond by hexamethylphosphoric triamide: synthesis and characterization of [SiCl3(HMPA)3]+[Fe(CO)4SiCl3]-. Z. Naturforsch. , B: J. Chem. Sci. 2009, 64, 1553-1557.

(33) Shriver, D. F.; Drezdzon, M. A. In The Manipulation of Air-sensitive Compounds; John Wiley and Sons: New York, 1986; Vol. 2, pp 325.

(34) Pi, Z. Solvent Coordinated Silylium Cations and Stabilized Transition Metal Silylenes, University of Akron, Akron, OH, 1996.

(35) Darensbourg, M. Y.; Slater, S. Alternate synthetic routes to the pentacarbonylhydrides of chromium, molybdenum, and tungsten. J. Am. Chem. Soc. 1981, 103, 5914-5915.

(36) Brisdon, A. K. In Inorganic Spectroscopic Methods; Evans, J., Ed.; Oxford Chemistry Primers; Oxford University Press: Oxford, 1998; Vol. 62, pp 91.

(37) Stchedroff, M. J.; Moberg, V.; Rodriguez, E.; Aliev, A. E.; Boettcher, J.; Steed, J. W.; Nordlander, E.; Monari, M.; Deeming, A. J. Synthesis, characterization and natural abundance 187Os NMR spectroscopy of hydride bridged triosmium clusters with chiral diphosphine ligands. Inorg. Chim. Acta 2006, 359, 926-937.

(38) Stosur, M.; Kochel, A.; Keller, A.; Szymanska-Buzar, T. Photochemical Reaction of Mo(CO)6 with Et2SiH2: Spectroscopic Characterization and Crystal Structure of the Bis{(Î¼-Î·2-

108

hydridodiethylsilyl)tetracarbonylmolybdenum(I)} Complex [{Mo(Î¼-Î·2-H- SiEt2)(CO)4}2]. Organometallics 2006, 25, 3791-3794.

(39) Williams, E. A. In Recent Advances in Silicon-29 NMR Spectroscopy; Webb, G. A., Ed.; 1983; Vol. 15, pp 266-268.

(40) Takeuchi, Y.; Takayama, T. In 29Si NMR spectroscopy of organosilicon compounds; Rappoport, Z., Apeloig, Y., Eds.; The chemistry of organic silicon compounds; John Wiley and Sons, Ltd.: New York, 1998; Vol. 2, pp 284-290.

(41) Wrackmeyer, B. In Applications of 29Si NMR Parameters; Webb, G. A., Ed.; Annual reports on NMR spectroscopy; Elsevier Ltd.: United Kingdom, 2006; Vol. 57, pp 9-25.

(42) Mitzel, N. W.; Lustig, C. The molecular and crystal structures of the

tris(dimethylamino)phosphoranes (Me2N)3P–X (X = BH3, CH2, NH or O). J. Chem. Soc. , Dalton Trans. 1999, 1999, 3177-3183.

(43) Kaftory, M.; Kapon, M.; Botoshansky, M. In In The structural chemistry of organosilicon compounds. Section Title: Organometallic and Organometalloidal Compounds; 1998; Vol. 2, pp 181-265.

(44) Lambert, J. B.; Zhang, S.; Stern, C. L.; Huffman, J. C. Crystal Structure of a Silyl Cation with No Coordination to Anion and Distant Coordination to Solvent. Science 1993, 260, pp. 1917-1918.

(45) Allcock, H. R. Phosphorus-Nitrogen Compounds. Cyclic, Linear, and High- Polymeric Systems. 1972, 498.

(46) AnonymousApogee Technology. http://www.apogeemems.com/home/home.html (accessed June, 2011).

(47) AnonymousCelo Nova Biosciences. http://www.celonova.com/index.html (accessed June, 2011).

(48) AnonymousParallel Solutions. http://www.parallelsolutionsinc.com/ (accessed June, 2011).

109

(49) Anonymous,technically, http://technically.com/ (accessed June, 2011).

(50) Allcock, H. R. Chemistry and Applications of Polyphosphazenes. 2003, 109- 187.

(51) De Jaeger, R.; Gleria, M. Poly(organophosphazene)s and related compounds: synthesis, properties and applications. Prog. Polym. Sci. 1998, 23, 179-276.

(52) Dubois, P.; Coulembier, O.; Raquez, J.; Editors Handbook of Ring-Opening Polymerization. 2009, 97-122.

(53) Burford, N.; Spinney, H. A.; Ferguson, M. J.; McDonald, R. Donor-rich and acceptor-rich pyridine-phosphadiazonium adducts: Diversifying the Lewis acceptor chemistry of phosphorus(iii). Chem. Commun. 2004, 2004, 2696- 2697.

(54) Burford, N.; Stanley Cameron, T.; Robertson, K. N.; Phillips, A. D.; Jenkins, H. A. Nitrogen ligands on a phosphinic Lewis acceptorincluding a 2,2′-dipyridyl chelate complex. Chem. Commun. 2000, 2000, 2087- 2088.

(55) Sennett, M. S.; Hagnauer, G. L.; Singler, R. E.; Davies, G. Kinetics and mechanism of the boron trichloride-catalyzed thermal ring-opening polymerization of hexachlorocyclotriphosphazene in 1,2,4-trichlorobenzene solution. Macromolecules 1986, 19, 959-964.

(56) Bode, H.; Bach, H. Phosphonitrile compounds. I. Phenyl derivatives of triphosphonitrile chloride. Ber. Dtsch. Chem. Ges. B 1942, 75B, 215-226.

(57) Kravchenko, E. A.; Levin, B. V.; Bananyarly, S. I.; Toktomatov, T. A. NQR study of compounds of phosphonitrile chlorides with antimony pentachloride and tantalum pentachloride. Koord. Khim. 1977, 3, 374-379.

(58) Heston, A. J.; Panzner, M. J.; Youngs, W. J.; Tessier, C. A. Lewis Acid

Adducts of [PCl2N];3. Inorg. Chem. 2005, 44, 6518-6520.

110

(59) Heston, A. J.; Panzner, M.; Youngs, W. J.; Tessier, C. A. Acid-Base Chemistry of [PCl2N]3. Phosphorus, Sulfur Silicon Relat. Elem. 2004, 179, 831-837.

(60) Rivard, E.; Huynh, K.; Lough, A. J.; Manners, I. Donor-Stabilized Cations and Imine Transfer from N-Silylphosphoranimines. J. Am. Chem. Soc. 2004, 126, 2286-2287.

(61) Huynh, K.; Lough, A. J.; Forgeron, M. A. M.; Bendle, M.; Soto, A. P.; Wasylishen, R. E.; Manners, I. Synthesis and Reactivity of Phosphine-

Stabilized Phosphoranimine Cations, [R3P·PR′2Ã®Â— + Â»NSiMe3] . J. Am. Chem. Soc. 2009, 131, 7905-7916.

(62) Boomishankar, R.; Ledger, J.; Guilbaud, J.; Campbell, N. L.; Bacsa, J.; Bonar-Law, R.; Khimyak, Y. Z.; Steiner, A. The N-donor stabilised cyclotriphosphazene hexacation [P3N3(DMAP)6]6+. Chem. Commun. (Cambridge, U. K. ) 2007, 5152-5154.

(63) Di Gregorio, F.; Marconi, W.; Caglioti, L. Mono- and polyanhydride formation by reaction of 2,2,4,4,6,6-hexachlorotriazatriphosphorine with carboxylic acid salts under mild conditions. J. Org. Chem. 1981, 46, 4569-4570.

(64) Walsh, E. J.; Kaluzene, S.; Jubach, T. The reactions of halocyclophosphazenes with dimethylsulfoxide. J. Inorg. Nucl. Chem. 1976, 38, 397-399.

(65) Gabler, D. G.; Haw, J. F. Hydrolysis chemistry of the chlorophosphazene cyclic trimer. Inorg. Chem. 1990, 29, 4018-4021.

(66) Dormoy, J. R.; Castro, B. Phosphorus-31 NMR study of the reaction of hexamethylphosphoric triamide with phosphorus oxychloride. Tetrahedron 1981, 37, 3699-3706.

(67) Kim, K.; Kim, J.; Seo, G. Phosphazenium chloride catalysts immobilized on SBA-15 mesoporous material and silica gel: new exceptionally active catalysts for the chlorination of organic acids. Chem. Commun. 2003, 2003, 372-373.

111

(68) Barnes, N. A.; Godfrey, S. M.; Halton, R. T. A.; Pritchard, R. G.; Safi, Z.; Sheffield, J. M. Preference for a C3 conformation in tris- dimethylaminophosphonium cations: a comparison of the reactions of (Me2N)3P with I-X (X = Cl, Br, I, CN). Dalton Trans. 2007, 3252-3258.

(69) Chaplin, A. B.; Harrison, J. A.; Dyson, P. J. Revisiting the Electronic Structure of Phosphazenes. Inorg. Chem. 2005, 44, 8407-8417.

(70) Dewar, M. J. S.; Lucken, E. A. C.; Whitehead, M. A. 490. The structure of the phosphonitrilic halides. Journal of the Chemical Society (Resumed) 1960, 1960, 2423-2429.

(71) Reed, A. E.; Schleyer, P. v. R. The anomeric effect with central atoms other than carbon. 2. Strong interactions between nonbonded substituents in mono- and polyfluorinated first- and second-row amines, FnAHmNH2. Inorg. Chem. 1988, 27, 3969-3987.

(72) Reed, A. E.; Schleyer, P. v. R. Chemical bonding in hypervalent molecules. The dominance of ionic bonding and negative hyperconjugation over d- orbital participation. J. Am. Chem. Soc. 1990, 112, 1434-1445.

(73) Abbott, A. P.; Malkov, A. V.; Zimmermann, N.; Raynor, J. B.; Ahmed, G.; Steele, J.; Kocovsky, P. Oxidation of Molybdenum(0) and Tungsten(0) Carbonyl Complexes with Silver Triflate. Organometallics 1997, 16, 3690- 3695.

(74) Pickett, C. J.; Pletcher, D. Electrochemical oxidation and reduction of binary metal carbonyls in aprotic solvents. J. Chem. Soc. , Dalton Trans. 1975, 1975, 879-886.

(75) Hudson, H. R.; Dillion, K. B.; Walker, B. J. In 31P NMR Data of Four Coordinate Phosphonium Salts and Betaines; Tebby, J. C., Ed.; Handbook of Phosphorus-31 Nuclear Magnetic Resonance Data; CRC Press: Boston, 1991; Vol. Vol. 1, pp 181-226.

(76) Bullen, G. J. An improved determination of the crystal structure of hexachlorocyclotriphosphazene (phosphonitrilic chloride). J. Chem. Soc. (A) Inorg. Phys. Theor. 1971, 1971, 1450-1453.

112

(77) Hazekamp, R.; Migchelsen, T.; Vos, A. Refinement of the structure of metastable phosphonitrilic chloride (PNCl2)4. Acta Crystallogr. 1962, 15, 539-543.

113

Appendix 1. Supplement Materials for Complex W(CO)4(HMPA)2

W(CO)4(HMPA)2

Table 1. Crystal data and structure refinement for C16H36N6O6P2W Empirical formula C16H36N6O6P2W Formula weight 654.30 Temperature 273(2) K Wavelength 0.71073 Å Crystal system Monoclinic Space group P2(1)/n Unit cell dimensions a = 8.6248(7) Å = 90° b = 20.6694(17) Å = 96.1580(10)° c = 15.3663(12) Å  = 90° Volume 2723.5(4) Å3 Z 4 Density (calculated) 1.596 Mg/m3 Absorption coefficient 4.397 mm-1 F(000) 1304 Crystal size 0.23 x 0.14 x 0.12 mm3 Theta range for data collection 1.66 to 26.30° Index ranges -10<=h<=10, -25<=k<=25, -19<=l<=19 114

Reflections collected 21109 Independent reflections 5519 [R(int) = 0.0537] Completeness to theta = 26.30° 99.9 % Absorption correction Semi-empirical from equivalents Max. and min. transmission 0.6205 and 0.4312 Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 5519 / 0 / 292 Goodness-of-fit on F2 1.042 Final R indices [I>2sigma(I)] R1 = 0.0331, wR2 = 0.0501 R indices (all data) R1 = 0.0473, wR2 = 0.0568 Largest diff. peak and hole 0.526 and -0.625 e.Å-3

Table 2. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x 103) for C16H36N6O6P2W. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. ______x y z U(eq) ______W(1) 9320(1) 1565(1) 8046(1) 29(1) P(1) 7906(1) -23(1) 7781(1) 34(1) P(2) 10193(2) 1875(1) 5883(1) 35(1) O(1) 8936(3) 543(1) 7679(2) 38(1) O(2) 9565(4) 1558(2) 6635(2) 42(1) O(3) 12867(4) 1299(2) 8709(3) 69(1) O(4) 8958(5) 1473(2) 10032(2) 68(1) O(5) 9976(4) 3028(2) 8363(3) 64(1) O(6) 5785(4) 2012(2) 7818(3) 72(1) N(1) 7068(5) -96(2) 8678(3) 45(1) N(2) 8995(4) -664(2) 7733(3) 40(1) N(3) 6435(5) 2(2) 7013(3) 48(1) N(4) 11462(5) 1396(2) 5505(3) 57(1) N(5) 11126(5) 2551(2) 6070(3) 51(1) N(6) 8741(5) 2004(2) 5137(3) 46(1) C(1) 5763(6) 331(3) 8843(4) 72(2) C(2) 7901(7) -341(3) 9483(3) 65(2) C(3) 8386(6) -1320(2) 7788(4) 58(2) C(4) 10680(6) -634(3) 7772(4) 72(2) C(5) 6534(6) 382(3) 6230(3) 70(2) C(6) 5052(6) -406(3) 6985(4) 88(2) C(7) 11233(8) 700(3) 5522(5) 105(3) C(8) 12668(6) 1603(3) 4951(4) 92(2) C(9) 12553(7) 2561(3) 6681(4) 84(2) C(10) 10455(7) 3179(3) 5874(4) 83(2)

115

C(11) 8939(7) 2077(4) 4211(3) 102(3) C(12) 7186(6) 2160(3) 5349(4) 78(2) C(13) 11599(6) 1377(2) 8416(3) 40(1) C(14) 9069(6) 1500(2) 9268(3) 43(1) C(15) 9742(5) 2470(3) 8244(3) 41(1) C(16) 7052(6) 1825 (2) 7861(3) 43(1) C(15)-W(1)-C(13) 88.88(19) C(16)-W(1)-C(13) 170.9(2)

Table 3. Bond lengths [Å] and angles [°] for C16H36N6O6P2W. ______W(1)-C(14) 1.917(5) W(1)-C(15) 1.923(5) W(1)-C(16) 2.019(5) C(14)-W(1)-O(2) 175.46(16) W(1)-C(13) 2.023(5) C(15)-W(1)-O(2) 97.23(16) W(1)-O(2) 2.202(3) C(16)-W(1)-O(2) 93.23(16) W(1)-O(1) 2.203(3) C(13)-W(1)-O(2) 94.74(16) P(1)-O(1) 1.487(3) C(14)-W(1)-O(1) 98.83(16) P(1)-N(2) 1.630(4) C(15)-W(1)-O(1) 173.70(16) P(1)-N(1) 1.631(4) C(16)-W(1)-O(1) 95.87(16) P(1)-N(3) 1.638(4) C(13)-W(1)-O(1) 90.18(15) P(2)-O(2) 1.481(3) O(2)-W(1)-O(1) 76.64(11) P(2)-N(5) 1.622(4) O(1)-P(1)-N(2) 106.28(19) P(2)-N(6) 1.626(4) O(1)-P(1)-N(1) 119.1(2) P(2)-N(4) 1.629(4) N(2)-P(1)-N(1) 105.8(2) O(3)-C(13) 1.149(5) O(1)-P(1)-N(3) 109.0(2) O(4)-C(14) 1.190(5) N(2)-P(1)-N(3) 113.5(2) O(5)-C(15) 1.181(5) N(1)-P(1)-N(3) 103.4(2) O(6)-C(16) 1.154(5) O(2)-P(2)-N(5) 117.3(2) N(1)-C(2) 1.454(6) O(2)-P(2)-N(6) 107.7(2) N(1)-C(1) 1.473(6) N(5)-P(2)-N(6) 108.3(2) N(2)-C(4) 1.449(5) O(2)-P(2)-N(4) 109.0(2) N(2)-C(3) 1.461(5) N(5)-P(2)-N(4) 104.3(2) N(3)-C(5) 1.449(6) N(6)-P(2)-N(4) 110.1(2) N(3)-C(6) 1.456(6) P(1)-O(1)-W(1) 143.37(18) N(4)-C(7) 1.452(6) P(2)-O(2)-W(1) 147.97(19) N(4)-C(8) 1.476(6) C(2)-N(1)-C(1) 112.3(4) N(5)-C(10) 1.441(6) C(2)-N(1)-P(1) 121.9(3) N(5)-C(9) 1.465(6) C(1)-N(1)-P(1) 120.4(3) N(6)-C(12) 1.450(6) C(4)-N(2)-C(3) 113.7(4) N(6)-C(11) 1.459(6) C(4)-N(2)-P(1) 123.0(3) C(14)-W(1)-C(15) 87.3(2) C(3)-N(2)-P(1) 122.7(3) C(14)-W(1)-C(16) 87.0(2) C(5)-N(3)-C(6) 114.2(4) C(15)-W(1)-C(16) 85.83(19) C(5)-N(3)-P(1) 120.3(4) C(14)-W(1)-C(13) 85.4(2) C(6)-N(3)-P(1) 124.9(4) 116

C(7)-N(4)-C(8) 113.8(5) C(12)-N(6)-P(2) 122.6(4) C(7)-N(4)-P(2) 119.9(4) C(11)-N(6)-P(2) 122.9(4) C(8)-N(4)-P(2) 124.8(4) O(3)-C(13)-W(1) 172.8(5) C(10)-N(5)-C(9) 114.3(5) O(4)-C(14)-W(1) 177.6(5) C(10)-N(5)-P(2) 124.0(4) O(5)-C(15)-W(1) 178.9(4) C(9)-N(5)-P(2) 119.5(4) O(6)-C(16)-W(1) 173.8(5) C(12)-N(6)-C(11) 113.9(4) ______Symmetry transformations used to generate equivalent atoms:

Table 4. Anisotropic displacement parameters (Å2x 103) for C16H36N6O6P2W. The anisotropic displacement factor exponent takes the form: -22[ h2 a*2U11 + ... + 2 h k a* b* U12 ] ______U11 U22 U33 U23 U13 U12 ______W(1) 30(1) 28(1) 30(1) 3(1) 2(1) 2(1) P(1) 35(1) 27(1) 41(1) 4(1) 8(1) 2(1) P(2) 33(1) 40(1) 32(1) 8(1) 2(1) -3(1) O(1) 45(2) 30(2) 41(2) 2(2) 12(2) -3(2) O(2) 54(2) 42(2) 31(2) 7(2) 6(2) -15(2) O(3) 36(2) 81(3) 87(3) 23(2) -5(2) 7(2) O(4) 86(3) 87(3) 34(2) 4(2) 14(2) 19(2) O(5) 72(3) 29(2) 85(3) -3(2) -18(2) 3(2) O(6) 38(2) 86(3) 94(3) 16(3) 9(2) 20(2) N(1) 43(3) 43(3) 52(3) 12(2) 20(2) 8(2) N(2) 36(2) 27(2) 58(3) 1(2) 7(2) 2(2) N(3) 37(3) 42(3) 63(3) 14(2) -7(2) 0(2) N(4) 44(3) 58(3) 71(3) 4(3) 13(3) 9(2) N(5) 52(3) 49(3) 51(3) 11(2) -2(2) -19(2) N(6) 36(2) 68(3) 32(2) 7(2) -2(2) 4(2) C(1) 74(4) 68(4) 84(5) 16(4) 48(4) 18(4) C(2) 86(5) 72(4) 41(4) 7(3) 19(3) 7(4) C(3) 55(4) 26(3) 91(5) -1(3) 2(3) 6(3) C(4) 46(4) 55(4) 116(6) 6(4) 20(4) 13(3) C(5) 71(4) 90(5) 47(4) 16(4) -11(3) -2(4) C(6) 57(4) 60(4) 138(7) 21(4) -28(4) -13(3) C(7) 100(6) 57(5) 164(8) -7(5) 41(5) 16(4) C(8) 52(4) 133(7) 97(6) 14(5) 38(4) 11(4) C(9) 83(5) 104(5) 59(4) 23(4) -20(4) -63(4) C(10) 81(5) 39(4) 134(7) 0(4) 34(5) -6(3) C(11) 98(6) 176(8) 30(4) 17(4) 7(4) 57(5) C(12) 39(4) 126(6) 68(4) 28(4) 1(3) 5(4) C(13) 35(3) 34(3) 52(3) 7(2) 3(3) -1(2) 117

C(14) 43(3) 39(3) 44(3) -3(3) 1(3) 11(2) C(15) 35(3) 45(3) 41(3) 8(3) -9(2) 7(3) C(16) 43(3) 35(3) 49(3) 5(2) 2(3) -6(2)

Table 5. Hydrogen coordinates ( x 104) and isotropic displacement parameters

(Å2x 10 3) for C16H36N6O6P2W. ______x y z U(eq) ______

H(1A) 4957 79 9066 109 H(1B) 5355 536 8307 109 H(1C) 6127 654 9264 109 H(2A) 8273 16 9848 98 H(2B) 8769 -598 9347 98 H(2C) 7211 -602 9787 98 H(3A) 8834 -1592 7374 87 H(3B) 7273 -1314 7657 87 H(3C) 8653 -1486 8368 87 H(4A) 11135 -862 8281 107 H(4B) 11011 -191 7804 107 H(4C) 11011 -831 7256 107 H(5A) 6522 100 5733 106 H(5B) 7485 627 6290 106 H(5C) 5661 672 6148 106 H(6A) 4136 -139 6919 132 H(6B) 5077 -648 7519 132 H(6C) 5032 -698 6499 132 H(7A) 10867 551 4944 158 H(7B) 10476 597 5916 158 H(7C) 12204 492 5717 158 H(8A) 13670 1453 5203 138 H(8B) 12676 2066 4915 138 H(8C) 12441 1423 4375 138 H(9A) 13373 2766 6407 126 H(9B) 12853 2125 6838 126 H(9C) 12367 2797 7198 126 H(10A) 10226 3384 6407 125 H(10B) 9511 3132 5488 125 H(10C) 11181 3441 5597 125 H(11A) 8069 1885 3863 152 H(11B) 9885 1867 4089 152 H(11C) 8994 2529 4071 152 H(12A) 6884 2576 5112 117 118

H(12B) 7181 2168 5974 117 H(12C) 6465 1838 5104 117 ______

119

+ - Appendix 2. Supplemental Material for [SiEt3(HMPA) ][B(C6F5)4 ]

+ - [SiEt3(HMPA) ][B(C6F5)4 ]

120

+ [SiEt3(HMPA) ] disorder Major (~62.5%)

121

+ [SiEt3(HMPA) ] disorder Minor (~37.5%)

+ - Table 1. Crystal data and structure refinement for [SiEt3(HMPA) ][B(C6F5)4 ] Empirical formula C36H33BF20N3OPSi Formula weight 973.52 Temperature 100(2) K Wavelength 0.71073 Å Crystal system Triclinic Space group P-1 Unit cell dimensions a = 10.5130(7) Å = 84.3050(10)° b = 13.4013(9) Å = 88.2140(10)° c = 14.4258(10) Å  = 81.5810(10)° Volume 2000.3(2) Å3 122

Z 2 Density (calculated) 1.616 Mg/m3 Absorption coefficient 0.228 mm-1 F(000) 984 Crystal size 0.33 x 0.22 x 0.08 mm3 Theta range for data collection 1.42 to 25.00°. Index ranges -12<=h<=12, -15<=k<=15, -16<=l<=17 Reflections collected 14613 Independent reflections 7021 [R(int) = 0.0265] Completeness to theta = 25.00° 99.6 % Absorption correction Semi-empirical from equivalents Max. and min. transmission 0.9820 and 0.9285 Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 7021 / 0 / 597 Goodness-of-fit on F2 1.016 Final R indices [I>2sigma(I)] R1 = 0.0381, wR2 = 0.0767 R indices (all data) R1 = 0.0554, wR2 = 0.0847 Largest diff. peak and hole 0.294 and -0.333 e.Å-3

Table 2. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x 103) for C36H33BF20N3OPSi. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. ______x y z U(eq) ______P(1) 5844(1) 7515(1) 2169(1) 20(1) Si(1) 7352(1) 5370(1) 2619(1) 28(1) F(1) 3901(1) 2567(1) 4141(1) 28(1) F(2) 6441(1) 2092(1) 4053(1) 36(1) F(3) 7610(1) 1237(1) 2543(1) 38(1) F(4) 6133(1) 817(1) 1154(1) 33(1) F(5) 3603(1) 1234(1) 1235(1) 24(1) F(6) 2088(1) 198(1) 2598(1) 23(1) F(7) 576(1) -678(1) 1571(1) 29(1) F(8) -1175(1) 487(1) 406(1) 30(1) F(9) -1388(1) 2541(1) 318(1) 33(1) F(10) 38(1) 3429(1) 1365(1) 27(1) F(11) 3098(1) 632(1) 4316(1) 28(1) F(12) 1837(2) 49(1) 5830(1) 39(1) F(13) -559(2) 1001(1) 6240(1) 44(1) F(14) -1691(1) 2552(1) 5029(1) 38(1) F(15) -500(1) 3086(1) 3437(1) 28(1) F(16) 1377(1) 3983(1) 4158(1) 30(1) 123

F(17) 1443(2) 5938(1) 3729(1) 44(1) F(18) 2184(2) 6661(1) 1994(1) 50(1) F(19) 2858(2) 5341(1) 679(1) 43(1) F(20) 2736(1) 3371(1) 1071(1) 28(1) O(1) 6181(2) 6350(1) 2284(1) 25(1) N(1) 4854(2) 7736(1) 1316(1) 23(1) N(2) 7072(2) 8111(2) 1956(1) 30(1) N(3) 5202(2) 7871(1) 3135(1) 26(1) C(1) 8765(3) 5738(2) 894(2) 52(1) C(2) 8833(3) 5588(2) 1958(2) 36(1) C(3) 7598(2) 5385(2) 3885(2) 33(1) C(4) 6528(3) 5057(3) 4523(2) 58(1) C(5A) 6515(6) 4234(4) 2485(5) 29(1) C(6A) 6091(6) 4092(3) 1523(4) 34(2) C(5B) 6958(10) 4253(7) 2101(8) 29(2) C(6B) 5476(8) 4280(5) 2070(8) 37(3) C(7) 4879(2) 7117(2) 527(2) 28(1) C(8) 4049(3) 8727(2) 1166(2) 44(1) C(9) 7467(3) 8454(2) 1008(2) 43(1) C(10) 8022(3) 8182(2) 2667(2) 46(1) C(11) 5202(3) 8880(2) 3458(2) 40(1) C(12) 4181(3) 7336(2) 3583(2) 43(1) C(13) 3590(2) 1910(2) 2711(2) 20(1) C(14) 4412(2) 2105(2) 3388(2) 22(1) C(15) 5731(2) 1876(2) 3360(2) 25(1) C(16) 6319(2) 1442(2) 2607(2) 26(1) C(17) 5568(2) 1239(2) 1907(2) 23(1) C(18) 4247(2) 1463(2) 1973(2) 20(1) C(19) 1173(2) 1864(2) 2037(2) 19(1) C(20) 1229(2) 814(2) 2040(2) 19(1) C(21) 472(2) 343(2) 1512(2) 21(1) C(22) -409(2) 924(2) 924(2) 23(1) C(23) -517(2) 1962(2) 883(2) 22(1) C(24) 254(2) 2400(2) 1436(2) 20(1) C(25) 1385(2) 1927(2) 3797(2) 20(1) C(26) 1901(2) 1146(2) 4444(2) 23(1) C(27) 1269(2) 821(2) 5244(2) 27(1) C(28) 59(2) 1295(2) 5451(2) 30(1) C(29) -512(2) 2070(2) 4834(2) 28(1) C(30) 138(2) 2341(2) 4029(2) 23(1) C(31) 2006(2) 3559(2) 2626(2) 21(1) C(32) 1737(2) 4263(2) 3272(2) 26(1) C(33) 1788(2) 5294(2) 3074(2) 31(1) C(34) 2155(3) 5660(2) 2199(2) 34(1) C(35) 2474(2) 4997(2) 1539(2) 32(1) C(36) 2397(2) 3981(2) 1764(2) 25(1) 124

B(1) 2032(3) 2313(2) 2795(2) 20(1)

Table 3. Bond lengths [Å] and angles [°] for C36H33BF20N3OPSi ______P(1)-O(1) 1.5428(15) C(5B)-C(6B) 1.555(15) P(1)-N(1) 1.6124(19) C(13)-C(18) 1.389(3) P(1)-N(3) 1.614(2) C(13)-C(14) 1.392(3) P(1)-N(2) 1.621(2) C(13)-B(1) 1.652(3) Si(1)-O(1) 1.7070(16) C(14)-C(15) 1.376(3) Si(1)-C(5B) 1.843(10) C(15)-C(16) 1.371(3) Si(1)-C(2) 1.846(3) C(16)-C(17) 1.372(3) Si(1)-C(3) 1.854(3) C(17)-C(18) 1.380(3) Si(1)-C(5A) 1.894(6) C(19)-C(24) 1.387(3) F(1)-C(14) 1.360(2) C(19)-C(20) 1.398(3) F(2)-C(15) 1.344(3) C(19)-B(1) 1.652(3) F(3)-C(16) 1.348(3) C(20)-C(21) 1.375(3) F(4)-C(17) 1.354(2) C(21)-C(22) 1.375(3) F(5)-C(18) 1.362(2) C(22)-C(23) 1.373(3) F(6)-C(20) 1.358(2) C(23)-C(24) 1.383(3) F(7)-C(21) 1.351(2) C(25)-C(26) 1.390(3) F(8)-C(22) 1.347(2) C(25)-C(30) 1.391(3) F(9)-C(23) 1.348(2) C(25)-B(1) 1.647(3) F(10)-C(24) 1.359(2) C(26)-C(27) 1.378(3) F(11)-C(26) 1.360(3) C(27)-C(28) 1.374(3) F(12)-C(27) 1.348(3) C(28)-C(29) 1.377(4) F(13)-C(28) 1.347(3) C(29)-C(30) 1.374(3) F(14)-C(29) 1.346(3) C(31)-C(32) 1.386(3) F(15)-C(30) 1.360(3) C(31)-C(36) 1.389(3) F(16)-C(32) 1.355(3) C(31)-B(1) 1.660(3) F(17)-C(33) 1.348(3) C(32)-C(33) 1.391(3) F(18)-C(34) 1.349(3) C(33)-C(34) 1.373(4) F(19)-C(35) 1.351(3) C(34)-C(35) 1.367(4) F(20)-C(36) 1.360(3) C(35)-C(36) 1.382(3) N(1)-C(8) 1.467(3) O(1)-P(1)-N(1) 104.07(9) N(1)-C(7) 1.471(3) O(1)-P(1)-N(3) 107.99(10) N(2)-C(9) 1.466(3) N(1)-P(1)-N(3) 112.86(10) N(2)-C(10) 1.473(3) O(1)-P(1)-N(2) 114.29(10) N(3)-C(12) 1.474(3) N(1)-P(1)-N(2) 111.11(11) N(3)-C(11) 1.474(3) N(3)-P(1)-N(2) 106.63(10) C(1)-C(2) 1.532(4) O(1)-Si(1)-C(5B) 106.5(3) C(3)-C(4) 1.518(4) O(1)-Si(1)-C(2) 107.54(10) C(5A)-C(6A) 1.510(9) C(5B)-Si(1)-C(2) 100.7(4)

125

O(1)-Si(1)-C(3) 107.79(10) C(22)-C(21)-C(20) 119.2(2) C(5B)-Si(1)-C(3) 123.0(4) F(8)-C(22)-C(23) 120.1(2) C(2)-Si(1)-C(3) 110.26(12) F(8)-C(22)-C(21) 120.7(2) O(1)-Si(1)-C(5A) 101.59(19) C(23)-C(22)-C(21) 119.2(2) C(2)-Si(1)-C(5A) 122.1(2) F(9)-C(23)-C(22) 119.8(2) C(3)-Si(1)-C(5A) 106.5(2) F(9)-C(23)-C(24) 120.7(2) P(1)-O(1)-Si(1) 144.11(11) C(22)-C(23)-C(24) 119.5(2) C(8)-N(1)-C(7) 113.85(19) F(10)-C(24)-C(23) 114.64(19) C(8)-N(1)-P(1) 119.66(16) F(10)-C(24)-C(19) 120.75(19) C(7)-N(1)-P(1) 124.95(15) C(23)-C(24)-C(19) 124.6(2) C(9)-N(2)-C(10) 113.6(2) C(26)-C(25)-C(30) 112.8(2) C(9)-N(2)-P(1) 122.53(18) C(26)-C(25)-B(1) 127.4(2) C(10)-N(2)-P(1) 122.87(18) C(30)-C(25)-B(1) 119.5(2) C(12)-N(3)-C(11) 112.9(2) F(11)-C(26)-C(27) 114.7(2) C(12)-N(3)-P(1) 118.91(17) F(11)-C(26)-C(25) 121.0(2) C(11)-N(3)-P(1) 124.86(17) C(27)-C(26)-C(25) 124.3(2) C(1)-C(2)-Si(1) 117.8(2) F(12)-C(27)-C(28) 119.8(2) C(4)-C(3)-Si(1) 115.84(19) F(12)-C(27)-C(26) 120.4(2) C(6A)-C(5A)-Si(1) 117.7(5) C(28)-C(27)-C(26) 119.8(2) C(6B)-C(5B)-Si(1) 110.5(7) F(13)-C(28)-C(27) 120.5(2) C(18)-C(13)-C(14) 112.6(2) F(13)-C(28)-C(29) 120.7(2) C(18)-C(13)-B(1) 127.3(2) C(27)-C(28)-C(29) 118.8(2) C(14)-C(13)-B(1) 119.74(19) F(14)-C(29)-C(30) 121.0(2) F(1)-C(14)-C(15) 115.9(2) F(14)-C(29)-C(28) 119.8(2) F(1)-C(14)-C(13) 119.0(2) C(30)-C(29)-C(28) 119.2(2) C(15)-C(14)-C(13) 125.2(2) F(15)-C(30)-C(29) 116.1(2) F(2)-C(15)-C(16) 120.1(2) F(15)-C(30)-C(25) 119.0(2) F(2)-C(15)-C(14) 120.6(2) C(29)-C(30)-C(25) 124.9(2) C(16)-C(15)-C(14) 119.2(2) C(32)-C(31)-C(36) 112.9(2) F(3)-C(16)-C(15) 120.8(2) C(32)-C(31)-B(1) 128.0(2) F(3)-C(16)-C(17) 120.4(2) C(36)-C(31)-B(1) 118.86(19) C(15)-C(16)-C(17) 118.8(2) F(16)-C(32)-C(31) 121.1(2) F(4)-C(17)-C(16) 119.6(2) F(16)-C(32)-C(33) 114.9(2) F(4)-C(17)-C(18) 120.4(2) C(31)-C(32)-C(33) 124.0(2) C(16)-C(17)-C(18) 120.1(2) F(17)-C(33)-C(34) 119.9(2) F(5)-C(18)-C(17) 114.82(19) F(17)-C(33)-C(32) 120.3(2) F(5)-C(18)-C(13) 121.00(19) C(34)-C(33)-C(32) 119.8(2) C(17)-C(18)-C(13) 124.2(2) F(18)-C(34)-C(35) 120.8(2) C(24)-C(19)-C(20) 112.6(2) F(18)-C(34)-C(33) 120.3(2) C(24)-C(19)-B(1) 127.93(19) C(35)-C(34)-C(33) 119.0(2) C(20)-C(19)-B(1) 119.01(19) F(19)-C(35)-C(34) 119.8(2) F(6)-C(20)-C(21) 116.31(19) F(19)-C(35)-C(36) 120.9(2) F(6)-C(20)-C(19) 118.78(19) C(34)-C(35)-C(36) 119.3(2) C(21)-C(20)-C(19) 124.9(2) F(20)-C(36)-C(35) 115.6(2) F(7)-C(21)-C(22) 119.9(2) F(20)-C(36)-C(31) 119.36(19) F(7)-C(21)-C(20) 120.9(2) C(35)-C(36)-C(31) 125.0(2) 126

C(25)-B(1)-C(19) 102.19(18) C(25)-B(1)-C(31) 113.88(18) C(25)-B(1)-C(13) 113.24(18) C(19)-B(1)-C(31) 113.44(18) C(19)-B(1)-C(13) 113.35(18) C(13)-B(1)-C(31) 101.25(18) ______Symmetry transformations used to generate equivalent atoms:

127

Table 4. Anisotropic displacement parameters (Å2x 103) for C36H33BF20N3OPSi. The anisotropic displacement factor exponent takes the form: -22[ h2 a*2U11 + ... + 2 h k a* b* U12 ] ______U11 U22 U33 U23 U13 U12 ______P(1) 20(1) 18(1) 23(1) -2(1) 0(1) -1(1) Si(1) 36(1) 17(1) 30(1) -2(1) -14(1) 0(1) F(1) 31(1) 32(1) 22(1) -10(1) -3(1) -2(1) F(2) 29(1) 49(1) 31(1) -2(1) -11(1) -11(1) F(3) 19(1) 54(1) 36(1) 8(1) 1(1) -1(1) F(4) 30(1) 40(1) 27(1) -3(1) 9(1) 5(1) F(5) 28(1) 26(1) 18(1) -5(1) 0(1) -2(1) F(6) 26(1) 18(1) 24(1) 0(1) -2(1) -1(1) F(7) 37(1) 20(1) 31(1) -3(1) 0(1) -9(1) F(8) 25(1) 37(1) 31(1) -8(1) -3(1) -11(1) F(9) 27(1) 36(1) 36(1) -2(1) -11(1) 4(1) F(10) 31(1) 18(1) 31(1) -3(1) -6(1) 3(1) F(11) 33(1) 23(1) 25(1) 1(1) 1(1) 5(1) F(12) 60(1) 31(1) 24(1) 7(1) -2(1) -9(1) F(13) 50(1) 63(1) 24(1) -3(1) 13(1) -27(1) F(14) 24(1) 61(1) 33(1) -20(1) 6(1) -9(1) F(15) 24(1) 30(1) 28(1) -6(1) -2(1) 2(1) F(16) 40(1) 26(1) 24(1) -9(1) 1(1) -3(1) F(17) 61(1) 24(1) 49(1) -17(1) -8(1) -1(1) F(18) 71(1) 18(1) 62(1) 2(1) -12(1) -14(1) F(19) 60(1) 31(1) 39(1) 12(1) 1(1) -16(1) F(20) 37(1) 25(1) 22(1) 0(1) 3(1) -4(1) O(1) 28(1) 17(1) 30(1) -1(1) -7(1) -1(1) N(1) 25(1) 22(1) 21(1) 0(1) -1(1) 2(1) N(2) 31(1) 28(1) 35(1) -9(1) 3(1) -12(1) N(3) 29(1) 27(1) 23(1) -5(1) 1(1) 0(1) C(1) 71(2) 43(2) 33(2) 0(1) 1(2) 22(2) C(2) 43(2) 29(1) 31(2) -9(1) -5(1) 16(1) C(3) 32(2) 33(2) 33(2) 4(1) -7(1) -6(1) C(4) 39(2) 82(2) 46(2) 27(2) -7(2) -9(2) C(5A) 30(4) 17(2) 39(4) -1(2) -9(2) -2(2) C(6A) 42(3) 32(3) 31(3) -4(2) -7(2) -15(2) C(5B) 21(5) 20(4) 45(7) -3(4) 5(4) -1(4) C(6B) 27(5) 22(4) 61(7) -2(4) -2(5) -4(3) C(7) 34(1) 27(1) 24(1) 0(1) -5(1) -7(1) C(8) 53(2) 41(2) 30(2) -7(1) -7(1) 22(1) C(9) 47(2) 36(2) 51(2) -11(1) 22(1) -19(1) C(10) 34(2) 39(2) 71(2) -18(2) -7(2) -14(1) C(11) 54(2) 34(2) 31(2) -12(1) -2(1) 9(1) 128

C(12) 39(2) 62(2) 30(2) 0(1) 8(1) -12(1) C(13) 26(1) 15(1) 18(1) 2(1) -1(1) -3(1) C(14) 29(1) 19(1) 19(1) -2(1) 0(1) -3(1) C(15) 27(1) 28(1) 20(1) 3(1) -7(1) -8(1) C(16) 17(1) 31(1) 28(1) 8(1) 1(1) -1(1) C(17) 26(1) 23(1) 18(1) 2(1) 5(1) -1(1) C(18) 23(1) 18(1) 19(1) 2(1) -3(1) -3(1) C(19) 19(1) 19(1) 18(1) -2(1) 5(1) -1(1) C(20) 18(1) 22(1) 15(1) -1(1) 3(1) 0(1) C(21) 25(1) 17(1) 23(1) -4(1) 5(1) -5(1) C(22) 18(1) 33(1) 20(1) -8(1) 3(1) -9(1) C(23) 18(1) 28(1) 20(1) -1(1) -2(1) 2(1) C(24) 22(1) 15(1) 22(1) -4(1) 3(1) 1(1) C(25) 25(1) 18(1) 19(1) -6(1) 0(1) -4(1) C(26) 29(1) 22(1) 21(1) -5(1) 0(1) -4(1) C(27) 41(2) 23(1) 18(1) 0(1) -4(1) -11(1) C(28) 36(2) 40(2) 19(1) -5(1) 8(1) -22(1) C(29) 21(1) 41(2) 24(1) -16(1) 5(1) -11(1) C(30) 25(1) 22(1) 22(1) -7(1) -4(1) -4(1) C(31) 22(1) 18(1) 23(1) -1(1) -4(1) -2(1) C(32) 27(1) 24(1) 26(1) -3(1) -3(1) -3(1) C(33) 37(2) 20(1) 37(2) -11(1) -7(1) -3(1) C(34) 43(2) 15(1) 46(2) 2(1) -10(1) -8(1) C(35) 36(2) 29(1) 30(2) 5(1) -2(1) -10(1) C(36) 26(1) 20(1) 28(1) -3(1) -1(1) -2(1) B(1) 24(1) 18(1) 17(1) -1(1) 0(1) -2(1)

Table 5. Hydrogen coordinates ( x 104) and isotropic displacement parameters

(Å2x 10 3) for C36H33BF20N3OPSi. ______x y z U(eq) ______H(1A) 8615 5118 662 79 H(1B) 9562 5923 639 79 H(1C) 8074 6266 712 79 H(2A) 9120 6183 2167 43 H(2B) 9491 5017 2125 43 H(3A) 8391 4945 4051 40 H(3B) 7710 6067 4002 40 H(4A) 5730 5474 4357 87 H(4B) 6721 5128 5157 87 H(4C) 6457 4361 4458 87 H(5A1) 7090 3630 2708 35 H(5A2) 5762 4276 2894 35 H(6A1) 5507 4677 1292 50 129

H(6A2) 5668 3502 1552 50 H(6A3) 6828 4008 1113 50 H(5B1) 7319 4241 1474 35 H(5B2) 7337 3640 2466 35 H(6B1) 5120 4294 2690 55 H(6B2) 5288 3687 1809 55 H(6B3) 5106 4875 1691 55 H(7A) 4017 7031 388 42 H(7B) 5377 6466 686 42 H(7C) 5261 7450 -8 42 H(8A) 4426 9139 681 66 H(8B) 3990 9054 1732 66 H(8C) 3204 8636 988 66 H(9A) 7598 9150 982 65 H(9B) 6808 8390 581 65 H(9C) 8253 8047 841 65 H(10A) 8840 7823 2497 69 H(10B) 7743 7890 3260 69 H(10C) 8101 8881 2708 69 H(11A) 4348 9249 3425 61 H(11B) 5774 9243 3070 61 H(11C) 5485 8806 4091 61 H(12A) 4285 7263 4246 65 H(12B) 4239 6678 3362 65 H(12C) 3356 7718 3433 65 ______

130

+ - Appendix 3. Supplemental Material for [P(NMe2)3Cl ][B(C6F5)4 ]

+ - [P(NMe2)3Cl ][B(C6F5)4 ]

131

+ [P(NMe2)3Cl ]

+ - Table 1. Crystal data and structure refinement for [P(NMe2)3Cl ][B(C6F5)4 ] Empirical formula C30H18BClF20N3P Formula weight 877.70 Temperature 100(2) K Wavelength 0.71073 Å Crystal system Triclinic Space group P-1 Unit cell dimensions a = 8.0635(8) Å = 93.366(2)° b = 19.9748(19) Å = 97.962(2)° c = 20.647(2) Å  = 93.253(2)°

132

Volume 3280.6(6) Å3 Z 4 Density (calculated) 1.777 Mg/m3 Absorption coefficient 0.310 mm-1 F(000) 1744 Crystal size 0.32 x 0.17 x 0.15 mm3 Theta range for data collection 1.02 to 26.30°. Index ranges -10<=h<=10, -24<=k<=24, -25<=l<=25 Reflections collected 26581 Independent reflections 13164 [R(int) = 0.0314] Completeness to theta = 26.30° 99.1 % Absorption correction Semi-empirical from equivalents Max. and min. transmission 0.9550 and 0.9074 Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 13164 / 0 / 1021 Goodness-of-fit on F2 1.086 Final R indices [I>2sigma(I)] R1 = 0.0427, wR2 = 0.1071 R indices (all data) R1 = 0.0613, wR2 = 0.1130 Largest diff. peak and hole 0.414 and -0.434 e.Å-3

Table 2. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x 103) for C30H18BClF20N3P. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. ______x y z U(eq) ______Cl(1) 6194(1) 2648(1) 957(1) 39(1) Cl(2) 3784(1) 2322(1) 4239(1) 32(1) P(1) 4208(1) 2313(1) 277(1) 23(1) P(2) 5858(1) 2676(1) 4868(1) 19(1) F(1) 4297(2) 3578(1) 2066(1) 27(1) F(2) 2279(2) 2842(1) 2678(1) 31(1) F(3) 697(2) 3404(1) 3642(1) 34(1) F(4) 1216(2) 4748(1) 3973(1) 34(1) F(5) 3267(2) 5512(1) 3364(1) 27(1) F(6) 7509(2) 4088(1) 2702(1) 26(1) F(7) 9468(2) 3468(1) 1942(1) 32(1) F(8) 9408(2) 3757(1) 667(1) 35(1) F(9) 7296(2) 4681(1) 165(1) 32(1) F(10) 5401(2) 5314(1) 898(1) 28(1)

133

F(11) 6266(2) 5015(1) 3862(1) 28(1) F(12) 8883(2) 5673(1) 4572(1) 34(1) F(13) 10912(2) 6552(1) 4029(1) 34(1) F(14) 10209(2) 6755(1) 2730(1) 30(1) F(15) 7539(2) 6117(1) 1997(1) 25(1) F(16) 2516(2) 4685(1) 1313(1) 27(1) F(17) 273(2) 5440(1) 667(1) 32(1) F(18) 416(2) 6794(1) 949(1) 38(1) F(19) 2720(2) 7362(1) 1949(1) 36(1) F(20) 4849(2) 6627(1) 2631(1) 27(1) F(21) 5193(2) 8427(1) 2112(1) 29(1) F(22) 7384(2) 7618(1) 2641(1) 36(1) F(23) 9704(2) 8054(1) 3694(1) 38(1) F(24) 9735(2) 9346(1) 4207(1) 32(1) F(25) 7442(2) 10165(1) 3710(1) 26(1) F(26) 2535(2) 8756(1) 2854(1) 28(1) F(27) -107(2) 8181(1) 2049(1) 40(1) F(28) -964(2) 8622(1) 838(1) 51(1) F(29) 956(2) 9646(1) 436(1) 49(1) F(30) 3577(2) 10230(1) 1212(1) 37(1) F(31) 6669(2) 9688(1) 1578(1) 36(1) F(32) 8779(2) 10573(1) 1132(1) 47(1) F(33) 9333(2) 11848(1) 1703(1) 43(1) F(34) 7684(2) 12220(1) 2716(1) 37(1) F(35) 5594(2) 11368(1) 3164(1) 28(1) F(36) 4589(2) 9447(1) 4053(1) 24(1) F(37) 2823(2) 10022(1) 4897(1) 28(1) F(38) 804(2) 11023(1) 4543(1) 34(1) F(39) 616(2) 11453(1) 3312(1) 32(1) F(40) 2444(2) 10914(1) 2457(1) 27(1) N(1) 2756(2) 2112(1) 695(1) 27(1) N(2) 4815(2) 1697(1) -147(1) 32(1) N(3) 3725(2) 2913(1) -180(1) 29(1) N(4) 6367(2) 3411(1) 4659(1) 23(1) N(5) 7309(2) 2182(1) 4779(1) 23(1) N(6) 5316(2) 2679(1) 5588(1) 24(1) C(1) 3059(3) 1787(1) 1320(1) 37(1) C(2) 1000(3) 2263(1) 501(1) 38(1) C(3) 4346(4) 992(1) -43(1) 44(1) C(4) 6376(3) 1805(2) -442(1) 53(1) C(5) 3600(3) 2870(2) -899(1) 42(1) C(6) 3447(3) 3577(1) 126(1) 41(1) C(7) 6599(3) 3499(1) 3972(1) 30(1) C(8) 6194(3) 4037(1) 5048(1) 32(1) C(9) 9012(3) 2402(1) 4656(1) 32(1) C(10) 6980(3) 1446(1) 4779(1) 31(1) 134

C(11) 6218(3) 2333(1) 6132(1) 28(1) C(12) 3689(3) 2914(1) 5716(1) 39(1) C(13) 3980(3) 4586(1) 2706(1) 20(1) C(14) 3613(3) 3904(1) 2547(1) 22(1) C(15) 2543(3) 3504(1) 2855(1) 24(1) C(16) 1745(3) 3783(1) 3340(1) 25(1) C(17) 2005(3) 4464(1) 3502(1) 25(1) C(18) 3081(3) 4841(1) 3184(1) 22(1) C(19) 6296(3) 4721(1) 1842(1) 19(1) C(20) 7425(3) 4254(1) 2071(1) 21(1) C(21) 8468(3) 3937(1) 1695(1) 24(1) C(22) 8437(3) 4079(1) 1048(1) 25(1) C(23) 7371(3) 4536(1) 797(1) 24(1) C(24) 6350(3) 4850(1) 1192(1) 22(1) C(25) 6731(3) 5525(1) 2882(1) 19(1) C(26) 7182(3) 5443(1) 3541(1) 22(1) C(27) 8551(3) 5775(1) 3931(1) 25(1) C(28) 9574(3) 6219(1) 3658(1) 25(1) C(29) 9217(3) 6323(1) 3004(1) 23(1) C(30) 7831(3) 5983(1) 2635(1) 22(1) C(31) 3861(3) 5616(1) 1988(1) 19(1) C(32) 2607(3) 5349(1) 1492(1) 22(1) C(33) 1445(3) 5726(1) 1147(1) 25(1) C(34) 1508(3) 6411(1) 1292(1) 27(1) C(35) 2672(3) 6697(1) 1792(1) 25(1) C(36) 3793(3) 6299(1) 2132(1) 22(1) C(37) 6120(3) 9334(1) 2910(1) 21(1) C(38) 6237(3) 8682(1) 2654(1) 22(1) C(39) 7392(3) 8248(1) 2905(1) 26(1) C(40) 8562(3) 8469(1) 3436(1) 27(1) C(41) 8570(3) 9121(1) 3693(1) 25(1) C(42) 7375(3) 9532(1) 3429(1) 23(1) C(43) 3219(3) 9525(1) 2082(1) 23(1) C(44) 2186(3) 8998(1) 2253(1) 25(1) C(45) 808(3) 8695(1) 1852(1) 30(1) C(46) 377(3) 8919(1) 1241(1) 35(1) C(47) 1329(3) 9431(1) 1037(1) 35(1) C(48) 2714(3) 9721(1) 1456(1) 29(1) C(49) 5946(3) 10478(1) 2376(1) 22(1) C(50) 6858(3) 10322(1) 1870(1) 26(1) C(51) 7965(3) 10761(1) 1637(1) 33(1) C(52) 8243(3) 11409(1) 1918(1) 31(1) C(53) 7404(3) 11596(1) 2427(1) 27(1) C(54) 6299(3) 11132(1) 2645(1) 23(1) C(55) 3678(3) 10171(1) 3213(1) 20(1) C(56) 3675(3) 9962(1) 3841(1) 20(1) 135

C(57) 2746(3) 10241(1) 4292(1) 22(1) C(58) 1708(3) 10742(1) 4115(1) 24(1) C(59) 1611(3) 10956(1) 3489(1) 24(1) C(60) 2577(3) 10670(1) 3062(1) 22(1) B(1) 5202(3) 5109(1) 2356(1) 19(1) B(2) 4752(3) 9875(1) 2642(1) 21(1) ______

Table 3. Bond lengths [Å] and F(26)-C(44) 1.356(3) angles [°] for C30H18BClF20N3P F(27)-C(45) 1.345(3) ______F(28)-C(46) 1.354(3) ______F(29)-C(47) 1.339(3) Cl(1)-P(1) 2.0317(9) F(30)-C(48) 1.359(3) Cl(2)-P(2) 2.0357(8) F(31)-C(50) 1.361(3) P(1)-N(1) 1.5943(19) F(32)-C(51) 1.354(3) P(1)-N(3) 1.6016(19) F(33)-C(52) 1.345(3) P(1)-N(2) 1.608(2) F(34)-C(53) 1.344(3) P(2)-N(5) 1.5949(18) F(35)-C(54) 1.354(2) P(2)-N(4) 1.6020(18) F(36)-C(56) 1.358(2) P(2)-N(6) 1.6058(18) F(37)-C(57) 1.341(2) F(1)-C(14) 1.352(2) F(38)-C(58) 1.339(2) F(2)-C(15) 1.347(2) F(39)-C(59) 1.347(2) F(3)-C(16) 1.345(2) F(40)-C(60) 1.361(2) F(4)-C(17) 1.351(2) N(1)-C(2) 1.470(3) F(5)-C(18) 1.364(2) N(1)-C(1) 1.475(3) F(6)-C(20) 1.356(2) N(2)-C(3) 1.473(3) F(7)-C(21) 1.348(2) N(2)-C(4) 1.482(3) F(8)-C(22) 1.347(2) N(3)-C(5) 1.471(3) F(9)-C(23) 1.348(2) N(3)-C(6) 1.476(3) F(10)-C(24) 1.353(2) N(4)-C(8) 1.468(3) F(11)-C(26) 1.359(2) N(4)-C(7) 1.475(3) F(12)-C(27) 1.343(2) N(5)-C(9) 1.478(3) F(13)-C(28) 1.351(2) N(5)-C(10) 1.480(3) F(14)-C(29) 1.345(2) N(6)-C(12) 1.471(3) F(15)-C(30) 1.350(2) N(6)-C(11) 1.479(3) F(16)-C(32) 1.352(2) C(1)-H(1A) 0.9800 F(17)-C(33) 1.347(2) C(1)-H(1B) 0.9800 F(18)-C(34) 1.353(2) C(1)-H(1C) 0.9800 F(19)-C(35) 1.347(2) C(2)-H(2A) 0.9800 F(20)-C(36) 1.352(2) C(2)-H(2B) 0.9800 F(21)-C(38) 1.359(2) C(2)-H(2C) 0.9800 F(22)-C(39) 1.342(2) C(3)-H(3A) 0.9800 F(23)-C(40) 1.350(2) C(3)-H(3B) 0.9800 F(24)-C(41) 1.353(2) C(3)-H(3C) 0.9800 F(25)-C(42) 1.354(2) C(4)-H(4A) 0.9800 136

C(4)-H(4B) 0.9800 C(29)-C(30) 1.381(3) C(4)-H(4C) 0.9800 C(31)-C(36) 1.386(3) C(5)-H(5A) 0.9800 C(31)-C(32) 1.393(3) C(5)-H(5B) 0.9800 C(31)-B(1) 1.661(3) C(5)-H(5C) 0.9800 C(32)-C(33) 1.382(3) C(6)-H(6A) 0.9800 C(33)-C(34) 1.380(3) C(6)-H(6B) 0.9800 C(34)-C(35) 1.369(3) C(6)-H(6C) 0.9800 C(35)-C(36) 1.382(3) C(7)-H(7A) 0.9800 C(37)-C(38) 1.388(3) C(7)-H(7B) 0.9800 C(37)-C(42) 1.391(3) C(7)-H(7C) 0.9800 C(37)-B(2) 1.652(3) C(8)-H(8A) 0.9800 C(38)-C(39) 1.378(3) C(8)-H(8B) 0.9800 C(39)-C(40) 1.377(3) C(8)-H(8C) 0.9800 C(40)-C(41) 1.376(3) C(9)-H(9A) 0.9800 C(41)-C(42) 1.377(3) C(9)-H(9B) 0.9800 C(43)-C(48) 1.386(3) C(9)-H(9C) 0.9800 C(43)-C(44) 1.397(3) C(10)-H(10A) 0.9800 C(43)-B(2) 1.663(3) C(10)-H(10B) 0.9800 C(44)-C(45) 1.377(3) C(10)-H(10C) 0.9800 C(45)-C(46) 1.370(4) C(11)-H(11A) 0.9800 C(46)-C(47) 1.366(4) C(11)-H(11B) 0.9800 C(47)-C(48) 1.390(3) C(11)-H(11C) 0.9800 C(49)-C(54) 1.386(3) C(12)-H(12A) 0.9800 C(49)-C(50) 1.389(3) C(12)-H(12B) 0.9800 C(49)-B(2) 1.665(3) C(12)-H(12C) 0.9800 C(50)-C(51) 1.370(3) C(13)-C(14) 1.388(3) C(51)-C(52) 1.380(3) C(13)-C(18) 1.392(3) C(52)-C(53) 1.371(3) C(13)-B(1) 1.659(3) C(53)-C(54) 1.386(3) C(14)-C(15) 1.386(3) C(55)-C(56) 1.386(3) C(15)-C(16) 1.371(3) C(55)-C(60) 1.392(3) C(16)-C(17) 1.377(3) C(55)-B(2) 1.658(3) C(17)-C(18) 1.376(3) C(56)-C(57) 1.385(3) C(19)-C(24) 1.390(3) C(57)-C(58) 1.373(3) C(19)-C(20) 1.396(3) C(58)-C(59) 1.379(3) C(19)-B(1) 1.656(3) C(59)-C(60) 1.375(3) C(20)-C(21) 1.376(3) N(1)-P(1)-N(3) 112.08(10) C(21)-C(22) 1.379(3) N(1)-P(1)-N(2) 114.49(11) C(22)-C(23) 1.365(3) N(3)-P(1)-N(2) 110.20(11) C(23)-C(24) 1.385(3) N(1)-P(1)-Cl(1) 104.65(8) C(25)-C(26) 1.382(3) N(3)-P(1)-Cl(1) 108.23(8) C(25)-C(30) 1.404(3) N(2)-P(1)-Cl(1) 106.72(8) C(25)-B(1) 1.672(3) N(5)-P(2)-N(4) 110.44(10) C(26)-C(27) 1.383(3) N(5)-P(2)-N(6) 112.54(10) C(27)-C(28) 1.374(3) N(4)-P(2)-N(6) 113.25(9) C(28)-C(29) 1.372(3) N(5)-P(2)-Cl(2) 107.57(7) 137

N(4)-P(2)-Cl(2) 106.74(7) H(5A)-C(5)-H(5B) 109.5 N(6)-P(2)-Cl(2) 105.86(7) N(3)-C(5)-H(5C) 109.5 C(2)-N(1)-C(1) 114.15(19) H(5A)-C(5)-H(5C) 109.5 C(2)-N(1)-P(1) 122.44(16) H(5B)-C(5)-H(5C) 109.5 C(1)-N(1)-P(1) 123.36(16) N(3)-C(6)-H(6A) 109.5 C(3)-N(2)-C(4) 115.2(2) N(3)-C(6)-H(6B) 109.5 C(3)-N(2)-P(1) 122.00(17) H(6A)-C(6)-H(6B) 109.5 C(4)-N(2)-P(1) 118.20(18) N(3)-C(6)-H(6C) 109.5 C(5)-N(3)-C(6) 115.7(2) H(6A)-C(6)-H(6C) 109.5 C(5)-N(3)-P(1) 124.92(17) H(6B)-C(6)-H(6C) 109.5 C(6)-N(3)-P(1) 119.32(17) N(4)-C(7)-H(7A) 109.5 C(8)-N(4)-C(7) 114.80(17) N(4)-C(7)-H(7B) 109.5 C(8)-N(4)-P(2) 124.21(15) H(7A)-C(7)-H(7B) 109.5 C(7)-N(4)-P(2) 118.99(14) N(4)-C(7)-H(7C) 109.5 C(9)-N(5)-C(10) 114.92(17) H(7A)-C(7)-H(7C) 109.5 C(9)-N(5)-P(2) 124.45(15) H(7B)-C(7)-H(7C) 109.5 C(10)-N(5)-P(2) 120.56(16) N(4)-C(8)-H(8A) 109.5 C(12)-N(6)-C(11) 114.31(18) N(4)-C(8)-H(8B) 109.5 C(12)-N(6)-P(2) 121.28(15) H(8A)-C(8)-H(8B) 109.5 C(11)-N(6)-P(2) 123.38(15) N(4)-C(8)-H(8C) 109.5 N(1)-C(1)-H(1A) 109.5 H(8A)-C(8)-H(8C) 109.5 N(1)-C(1)-H(1B) 109.5 H(8B)-C(8)-H(8C) 109.5 H(1A)-C(1)-H(1B) 109.5 N(5)-C(9)-H(9A) 109.5 N(1)-C(1)-H(1C) 109.5 N(5)-C(9)-H(9B) 109.5 H(1A)-C(1)-H(1C) 109.5 H(9A)-C(9)-H(9B) 109.5 H(1B)-C(1)-H(1C) 109.5 N(5)-C(9)-H(9C) 109.5 N(1)-C(2)-H(2A) 109.5 H(9A)-C(9)-H(9C) 109.5 N(1)-C(2)-H(2B) 109.5 H(9B)-C(9)-H(9C) 109.5 H(2A)-C(2)-H(2B) 109.5 N(5)-C(10)-H(10A) 109.5 N(1)-C(2)-H(2C) 109.5 N(5)-C(10)-H(10B) 109.5 H(2A)-C(2)-H(2C) 109.5 H(10A)-C(10)-H(10B) 109.5 H(2B)-C(2)-H(2C) 109.5 N(5)-C(10)-H(10C) 109.5 N(2)-C(3)-H(3A) 109.5 H(10A)-C(10)-H(10C) 109.5 N(2)-C(3)-H(3B) 109.5 H(10B)-C(10)-H(10C) 109.5 H(3A)-C(3)-H(3B) 109.5 N(6)-C(11)-H(11A) 109.5 N(2)-C(3)-H(3C) 109.5 N(6)-C(11)-H(11B) 109.5 H(3A)-C(3)-H(3C) 109.5 H(11A)-C(11)-H(11B) 109.5 H(3B)-C(3)-H(3C) 109.5 N(6)-C(11)-H(11C) 109.5 N(2)-C(4)-H(4A) 109.5 H(11A)-C(11)-H(11C) 109.5 N(2)-C(4)-H(4B) 109.5 H(11B)-C(11)-H(11C) 109.5 H(4A)-C(4)-H(4B) 109.5 N(6)-C(12)-H(12A) 109.5 N(2)-C(4)-H(4C) 109.5 N(6)-C(12)-H(12B) 109.5 H(4A)-C(4)-H(4C) 109.5 H(12A)-C(12)-H(12B) 109.5 H(4B)-C(4)-H(4C) 109.5 N(6)-C(12)-H(12C) 109.5 N(3)-C(5)-H(5A) 109.5 H(12A)-C(12)-H(12C) 109.5 N(3)-C(5)-H(5B) 109.5 H(12B)-C(12)-H(12C) 109.5 138

C(14)-C(13)-C(18) 113.0(2) F(13)-C(28)-C(27) 120.5(2) C(14)-C(13)-B(1) 127.61(19) C(29)-C(28)-C(27) 119.3(2) C(18)-C(13)-B(1) 119.17(19) F(14)-C(29)-C(28) 120.0(2) F(1)-C(14)-C(15) 114.74(18) F(14)-C(29)-C(30) 120.7(2) F(1)-C(14)-C(13) 121.23(19) C(28)-C(29)-C(30) 119.3(2) C(15)-C(14)-C(13) 124.0(2) F(15)-C(30)-C(29) 116.25(19) F(2)-C(15)-C(16) 119.9(2) F(15)-C(30)-C(25) 119.32(19) F(2)-C(15)-C(14) 120.2(2) C(29)-C(30)-C(25) 124.4(2) C(16)-C(15)-C(14) 119.9(2) C(36)-C(31)-C(32) 113.61(19) F(3)-C(16)-C(15) 120.7(2) C(36)-C(31)-B(1) 126.97(19) F(3)-C(16)-C(17) 120.4(2) C(32)-C(31)-B(1) 119.38(18) C(15)-C(16)-C(17) 118.8(2) F(16)-C(32)-C(33) 116.34(19) F(4)-C(17)-C(18) 121.1(2) F(16)-C(32)-C(31) 119.49(19) F(4)-C(17)-C(16) 119.6(2) C(33)-C(32)-C(31) 124.1(2) C(18)-C(17)-C(16) 119.3(2) F(17)-C(33)-C(34) 119.5(2) F(5)-C(18)-C(17) 116.15(19) F(17)-C(33)-C(32) 121.4(2) F(5)-C(18)-C(13) 119.03(19) C(34)-C(33)-C(32) 119.1(2) C(17)-C(18)-C(13) 124.8(2) F(18)-C(34)-C(35) 120.5(2) C(24)-C(19)-C(20) 113.05(19) F(18)-C(34)-C(33) 120.3(2) C(24)-C(19)-B(1) 126.77(19) C(35)-C(34)-C(33) 119.2(2) C(20)-C(19)-B(1) 119.89(18) F(19)-C(35)-C(34) 119.9(2) F(6)-C(20)-C(21) 116.63(19) F(19)-C(35)-C(36) 120.4(2) F(6)-C(20)-C(19) 118.96(19) C(34)-C(35)-C(36) 119.7(2) C(21)-C(20)-C(19) 124.4(2) F(20)-C(36)-C(35) 114.91(19) F(7)-C(21)-C(20) 121.0(2) F(20)-C(36)-C(31) 121.07(19) F(7)-C(21)-C(22) 119.4(2) C(35)-C(36)-C(31) 124.0(2) C(20)-C(21)-C(22) 119.6(2) C(38)-C(37)-C(42) 113.17(19) F(8)-C(22)-C(23) 120.8(2) C(38)-C(37)-B(2) 127.28(19) F(8)-C(22)-C(21) 120.4(2) C(42)-C(37)-B(2) 119.48(18) C(23)-C(22)-C(21) 118.8(2) F(21)-C(38)-C(39) 114.36(19) F(9)-C(23)-C(22) 120.3(2) F(21)-C(38)-C(37) 120.89(19) F(9)-C(23)-C(24) 119.7(2) C(39)-C(38)-C(37) 124.7(2) C(22)-C(23)-C(24) 120.0(2) F(22)-C(39)-C(40) 120.0(2) F(10)-C(24)-C(23) 114.76(19) F(22)-C(39)-C(38) 121.0(2) F(10)-C(24)-C(19) 121.14(19) C(40)-C(39)-C(38) 119.0(2) C(23)-C(24)-C(19) 124.1(2) F(23)-C(40)-C(41) 120.4(2) C(26)-C(25)-C(30) 112.79(19) F(23)-C(40)-C(39) 120.3(2) C(26)-C(25)-B(1) 128.57(19) C(41)-C(40)-C(39) 119.2(2) C(30)-C(25)-B(1) 118.39(18) F(24)-C(41)-C(40) 119.6(2) F(11)-C(26)-C(25) 120.95(19) F(24)-C(41)-C(42) 120.9(2) F(11)-C(26)-C(27) 114.23(19) C(40)-C(41)-C(42) 119.4(2) C(25)-C(26)-C(27) 124.8(2) F(25)-C(42)-C(41) 116.42(19) F(12)-C(27)-C(28) 119.7(2) F(25)-C(42)-C(37) 119.29(19) F(12)-C(27)-C(26) 120.9(2) C(41)-C(42)-C(37) 124.3(2) C(28)-C(27)-C(26) 119.3(2) C(48)-C(43)-C(44) 113.0(2) F(13)-C(28)-C(29) 120.2(2) C(48)-C(43)-B(2) 128.0(2) 139

C(44)-C(43)-B(2) 118.82(19) F(39)-C(59)-C(60) 121.2(2) F(26)-C(44)-C(45) 116.2(2) F(39)-C(59)-C(58) 119.7(2) F(26)-C(44)-C(43) 119.14(19) C(60)-C(59)-C(58) 119.1(2) C(45)-C(44)-C(43) 124.7(2) F(40)-C(60)-C(59) 116.00(19) F(27)-C(45)-C(46) 119.7(2) F(40)-C(60)-C(55) 119.16(19) F(27)-C(45)-C(44) 121.1(2) C(59)-C(60)-C(55) 124.8(2) C(46)-C(45)-C(44) 119.2(2) C(19)-B(1)-C(13) 113.18(17) F(28)-C(46)-C(47) 120.4(2) C(19)-B(1)-C(31) 112.87(17) F(28)-C(46)-C(45) 120.0(2) C(13)-B(1)-C(31) 103.29(17) C(47)-C(46)-C(45) 119.6(2) C(19)-B(1)-C(25) 101.39(16) F(29)-C(47)-C(46) 120.6(2) C(13)-B(1)-C(25) 113.88(17) F(29)-C(47)-C(48) 120.0(2) C(31)-B(1)-C(25) 112.65(17) C(46)-C(47)-C(48) 119.4(2) C(37)-B(2)-C(55) 113.46(17) F(30)-C(48)-C(43) 120.7(2) C(37)-B(2)-C(43) 112.61(17) F(30)-C(48)-C(47) 115.1(2) C(55)-B(2)-C(43) 101.44(17) C(43)-C(48)-C(47) 124.2(2) C(37)-B(2)-C(49) 103.15(18) C(54)-C(49)-C(50) 113.1(2) C(55)-B(2)-C(49) 111.91(17) C(54)-C(49)-B(2) 127.36(19) C(43)-B(2)-C(49) 114.71(18) C(50)-C(49)-B(2) 119.25(19) ______F(31)-C(50)-C(51) 116.3(2) Symmetry transformations used to F(31)-C(50)-C(49) 118.9(2) generate equivalent atoms: C(51)-C(50)-C(49) 124.8(2) F(32)-C(51)-C(50) 121.1(2) F(32)-C(51)-C(52) 119.4(2) C(50)-C(51)-C(52) 119.5(2) F(33)-C(52)-C(53) 120.5(2) F(33)-C(52)-C(51) 120.6(2) C(53)-C(52)-C(51) 118.9(2) F(34)-C(53)-C(52) 119.8(2) F(34)-C(53)-C(54) 120.8(2) C(52)-C(53)-C(54) 119.4(2) F(35)-C(54)-C(53) 113.87(19) F(35)-C(54)-C(49) 121.73(19) C(53)-C(54)-C(49) 124.4(2) C(56)-C(55)-C(60) 113.24(19) C(56)-C(55)-B(2) 127.70(19) C(60)-C(55)-B(2) 119.01(18) F(36)-C(56)-C(57) 114.91(18) F(36)-C(56)-C(55) 121.01(19) C(57)-C(56)-C(55) 124.1(2) F(37)-C(57)-C(58) 119.38(19) F(37)-C(57)-C(56) 120.97(19) C(58)-C(57)-C(56) 119.64(19) F(38)-C(58)-C(57) 120.86(19) F(38)-C(58)-C(59) 120.1(2) C(57)-C(58)-C(59) 119.1(2) 140

Table 4. Anisotropic displacement parameters (Å2x 103) for C30H18BClF20N3P. The anisotropic displacement factor exponent takes the form: -22[ h2 a*2U11 + ... + 2 h k a* b* U12 ] ______U11 U22 U33 U23 U13 U12 ______Cl(1) 37(1) 36(1) 41(1) 2(1) -8(1) -7(1) Cl(2) 30(1) 31(1) 33(1) -3(1) -4(1) -2(1) P(1) 24(1) 23(1) 22(1) 4(1) 4(1) 3(1) P(2) 21(1) 17(1) 20(1) 1(1) 3(1) 3(1) F(1) 32(1) 23(1) 26(1) -5(1) 11(1) 0(1) F(2) 34(1) 20(1) 39(1) 0(1) 9(1) -6(1) F(3) 31(1) 34(1) 41(1) 11(1) 16(1) -3(1) F(4) 38(1) 36(1) 31(1) 3(1) 19(1) 7(1) F(5) 37(1) 21(1) 25(1) -2(1) 11(1) 4(1) F(6) 32(1) 26(1) 21(1) 5(1) 2(1) 7(1) F(7) 30(1) 29(1) 38(1) 1(1) 4(1) 11(1) F(8) 31(1) 40(1) 34(1) -6(1) 14(1) 7(1) F(9) 32(1) 49(1) 18(1) 3(1) 8(1) 4(1) F(10) 28(1) 37(1) 21(1) 10(1) 5(1) 9(1) F(11) 37(1) 26(1) 20(1) 7(1) 2(1) -2(1) F(12) 40(1) 38(1) 20(1) 3(1) -5(1) 4(1) F(13) 26(1) 38(1) 35(1) -7(1) -6(1) -2(1) F(14) 23(1) 30(1) 38(1) 1(1) 8(1) -3(1) F(15) 29(1) 27(1) 20(1) 5(1) 4(1) -2(1) F(16) 29(1) 23(1) 26(1) -3(1) 0(1) -1(1) F(17) 22(1) 46(1) 25(1) 3(1) -2(1) -1(1) F(18) 29(1) 42(1) 44(1) 16(1) 1(1) 12(1) F(19) 33(1) 21(1) 55(1) 4(1) 7(1) 7(1) F(20) 27(1) 20(1) 33(1) -3(1) 1(1) 2(1) F(21) 28(1) 23(1) 34(1) -5(1) 1(1) 4(1) F(22) 32(1) 18(1) 59(1) 0(1) 9(1) 5(1) F(23) 27(1) 35(1) 53(1) 18(1) 5(1) 11(1) F(24) 24(1) 41(1) 29(1) 8(1) -4(1) 0(1) F(25) 30(1) 23(1) 23(1) -2(1) 2(1) 0(1) F(26) 31(1) 27(1) 27(1) 4(1) 4(1) -1(1) F(27) 27(1) 41(1) 49(1) -11(1) 8(1) -7(1) F(28) 32(1) 66(1) 46(1) -18(1) -15(1) 7(1) F(29) 62(1) 56(1) 26(1) 2(1) -14(1) 22(1) F(30) 56(1) 30(1) 24(1) 8(1) 0(1) 6(1) F(31) 53(1) 30(1) 28(1) -2(1) 16(1) 9(1) F(32) 56(1) 54(1) 40(1) 10(1) 33(1) 16(1) F(33) 36(1) 45(1) 55(1) 20(1) 22(1) 1(1) F(34) 39(1) 25(1) 46(1) 1(1) 11(1) -6(1) F(35) 34(1) 24(1) 27(1) -2(1) 12(1) -1(1) 141

F(36) 28(1) 23(1) 22(1) 6(1) 4(1) 7(1) F(37) 35(1) 29(1) 20(1) 5(1) 7(1) 4(1) F(38) 38(1) 37(1) 33(1) 3(1) 17(1) 12(1) F(39) 33(1) 31(1) 34(1) 5(1) 6(1) 15(1) F(40) 34(1) 27(1) 22(1) 7(1) 5(1) 9(1) N(1) 28(1) 27(1) 27(1) 8(1) 7(1) 6(1) N(2) 34(1) 35(1) 28(1) -2(1) 6(1) 12(1) N(3) 31(1) 29(1) 31(1) 11(1) 8(1) 5(1) N(4) 31(1) 17(1) 20(1) 2(1) 5(1) 3(1) N(5) 27(1) 18(1) 26(1) 2(1) 9(1) 4(1) N(6) 24(1) 27(1) 23(1) 6(1) 7(1) 8(1) C(1) 47(2) 39(2) 29(1) 12(1) 11(1) 8(1) C(2) 29(1) 46(2) 42(2) 16(1) 12(1) 9(1) C(3) 63(2) 28(1) 36(2) -8(1) -7(1) 15(1) C(4) 38(2) 82(2) 42(2) -1(2) 16(1) 22(2) C(5) 32(2) 68(2) 32(1) 25(1) 11(1) 12(1) C(6) 43(2) 26(1) 53(2) 9(1) 1(1) 3(1) C(7) 41(2) 25(1) 25(1) 7(1) 8(1) 3(1) C(8) 53(2) 19(1) 25(1) -2(1) 5(1) 6(1) C(9) 31(1) 30(1) 37(1) 6(1) 13(1) 8(1) C(10) 41(2) 17(1) 35(1) 1(1) 5(1) 5(1) C(11) 31(1) 32(1) 24(1) 7(1) 5(1) 7(1) C(12) 36(2) 54(2) 32(1) 8(1) 14(1) 22(1) C(13) 21(1) 24(1) 16(1) 3(1) 1(1) 3(1) C(14) 23(1) 23(1) 18(1) 1(1) 1(1) 3(1) C(15) 25(1) 19(1) 26(1) 2(1) 0(1) 0(1) C(16) 21(1) 28(1) 26(1) 9(1) 5(1) -1(1) C(17) 25(1) 31(1) 20(1) 3(1) 7(1) 8(1) C(18) 26(1) 18(1) 22(1) 2(1) 3(1) 3(1) C(19) 20(1) 18(1) 19(1) -1(1) 1(1) -4(1) C(20) 23(1) 23(1) 17(1) 1(1) -1(1) -1(1) C(21) 20(1) 20(1) 31(1) 0(1) -1(1) 2(1) C(22) 21(1) 28(1) 27(1) -9(1) 10(1) -3(1) C(23) 24(1) 31(1) 17(1) 1(1) 2(1) -4(1) C(24) 20(1) 25(1) 20(1) 0(1) 2(1) -1(1) C(25) 22(1) 17(1) 20(1) 2(1) 3(1) 5(1) C(26) 28(1) 17(1) 22(1) 1(1) 5(1) 4(1) C(27) 29(1) 26(1) 17(1) 0(1) -1(1) 7(1) C(28) 20(1) 24(1) 30(1) -6(1) -3(1) 5(1) C(29) 20(1) 20(1) 30(1) 0(1) 6(1) 3(1) C(30) 26(1) 22(1) 18(1) 0(1) 3(1) 7(1) C(31) 18(1) 24(1) 17(1) 4(1) 5(1) 0(1) C(32) 23(1) 23(1) 21(1) 1(1) 9(1) -1(1) C(33) 18(1) 36(1) 22(1) 4(1) 3(1) 0(1) C(34) 19(1) 36(1) 29(1) 12(1) 7(1) 8(1) C(35) 23(1) 22(1) 34(1) 4(1) 11(1) 5(1) 142

C(36) 21(1) 25(1) 21(1) 2(1) 6(1) -1(1) C(37) 22(1) 19(1) 21(1) 4(1) 5(1) 2(1) C(38) 22(1) 22(1) 23(1) 1(1) 2(1) -1(1) C(39) 25(1) 16(1) 40(1) 4(1) 12(1) 2(1) C(40) 20(1) 28(1) 34(1) 14(1) 7(1) 7(1) C(41) 21(1) 32(1) 22(1) 7(1) 3(1) 0(1) C(42) 26(1) 21(1) 23(1) 1(1) 8(1) 0(1) C(43) 26(1) 21(1) 22(1) -1(1) 2(1) 9(1) C(44) 24(1) 25(1) 26(1) -2(1) 3(1) 7(1) C(45) 26(1) 30(1) 34(1) -6(1) 6(1) 7(1) C(46) 24(1) 41(2) 34(1) -14(1) -7(1) 11(1) C(47) 40(2) 39(2) 24(1) -3(1) -8(1) 19(1) C(48) 37(1) 22(1) 28(1) -1(1) 5(1) 9(1) C(49) 25(1) 23(1) 19(1) 5(1) 3(1) 5(1) C(50) 33(1) 26(1) 21(1) 3(1) 7(1) 6(1) C(51) 33(1) 42(2) 29(1) 10(1) 13(1) 12(1) C(52) 25(1) 34(1) 37(1) 16(1) 11(1) 4(1) C(53) 28(1) 23(1) 31(1) 5(1) 3(1) 1(1) C(54) 23(1) 25(1) 20(1) 3(1) 6(1) 5(1) C(55) 21(1) 16(1) 22(1) 0(1) 2(1) -2(1) C(56) 18(1) 16(1) 24(1) 1(1) 0(1) 1(1) C(57) 25(1) 22(1) 18(1) 2(1) 4(1) -4(1) C(58) 23(1) 23(1) 26(1) -2(1) 10(1) 2(1) C(59) 22(1) 18(1) 31(1) 4(1) 1(1) 3(1) C(60) 24(1) 21(1) 19(1) 2(1) 1(1) -1(1) B(1) 22(1) 17(1) 19(1) 2(1) 3(1) 1(1) B(2) 26(1) 17(1) 21(1) 3(1) 4(1) 4(1)

Table 5. Hydrogen coordinates ( x 104) and isotropic displacement parameters

(Å2x 10 3) for C30H18BClF20N3P. ______x y z U(eq) ______H(1A) 2910 2107 1682 56 H(1B) 4207 1641 1384 56 H(1C) 2261 1396 1309 56 H(2A) 895 2475 82 56 H(2B) 652 2569 838 56 H(2C) 282 1845 453 56 H(3A) 4242 722 -460 66 H(3B) 3270 966 128 66 H(3C) 5213 819 273 66 H(4A) 7303 1610 -173 79 H(4B) 6636 2288 -460 79 H(4C) 6220 1589 -886 79 143

H(5A) 2506 3013 -1090 63 H(5B) 3716 2405 -1056 63 H(5C) 4494 3162 -1031 63 H(6A) 4258 3915 6 61 H(6B) 3592 3558 603 61 H(6C) 2305 3697 -30 61 H(7A) 5636 3715 3751 44 H(7B) 6688 3059 3748 44 H(7C) 7627 3782 3962 44 H(8A) 7171 4348 5034 48 H(8B) 6125 3937 5503 48 H(8C) 5172 4242 4865 48 H(9A) 9847 2214 4974 47 H(9B) 9153 2894 4703 47 H(9C) 9164 2245 4211 47 H(10A) 7052 1238 4343 47 H(10B) 5854 1347 4892 47 H(10C) 7815 1266 5103 47 H(11A) 6421 2638 6528 43 H(11B) 7294 2199 6013 43 H(11C) 5539 1933 6214 43 H(12A) 2903 2526 5738 58 H(12B) 3240 3188 5362 58 H(12C) 3840 3185 6134 58

Table 6. Torsion angles [°] for C30H18BClF20N3P ______N(3)-P(1)-N(1)-C(2) 22.0(2) N(2)-P(1)-N(1)-C(2) -104.5(2) Cl(1)-P(1)-N(1)-C(2) 139.01(18) N(3)-P(1)-N(1)-C(1) -155.24(18) N(2)-P(1)-N(1)-C(1) 78.3(2) Cl(1)-P(1)-N(1)-C(1) -38.2(2) N(1)-P(1)-N(2)-C(3) -13.1(2) N(3)-P(1)-N(2)-C(3) -140.48(19) Cl(1)-P(1)-N(2)-C(3) 102.22(19) N(1)-P(1)-N(2)-C(4) -167.80(18) N(3)-P(1)-N(2)-C(4) 64.8(2) Cl(1)-P(1)-N(2)-C(4) -52.52(19) N(1)-P(1)-N(3)-C(5) -119.9(2) N(2)-P(1)-N(3)-C(5) 8.8(2) Cl(1)-P(1)-N(3)-C(5) 125.17(18) N(1)-P(1)-N(3)-C(6) 62.9(2) N(2)-P(1)-N(3)-C(6) -168.33(18)

144

Cl(1)-P(1)-N(3)-C(6) -51.98(19) N(5)-P(2)-N(4)-C(8) -133.42(18) N(6)-P(2)-N(4)-C(8) -6.2(2) Cl(2)-P(2)-N(4)-C(8) 109.94(18) N(5)-P(2)-N(4)-C(7) 63.52(19) N(6)-P(2)-N(4)-C(7) -169.23(16) Cl(2)-P(2)-N(4)-C(7) -53.13(18) N(4)-P(2)-N(5)-C(9) 11.9(2) N(6)-P(2)-N(5)-C(9) -115.73(19) Cl(2)-P(2)-N(5)-C(9) 128.05(17) N(4)-P(2)-N(5)-C(10) -164.75(16) N(6)-P(2)-N(5)-C(10) 67.60(19) Cl(2)-P(2)-N(5)-C(10) -48.63(18) N(5)-P(2)-N(6)-C(12) -160.02(18) N(4)-P(2)-N(6)-C(12) 73.8(2) Cl(2)-P(2)-N(6)-C(12) -42.8(2) N(5)-P(2)-N(6)-C(11) 7.7(2) N(4)-P(2)-N(6)-C(11) -118.41(18) Cl(2)-P(2)-N(6)-C(11) 124.97(17) C(18)-C(13)-C(14)-F(1) 176.22(18) B(1)-C(13)-C(14)-F(1) 1.5(3) C(18)-C(13)-C(14)-C(15) -3.7(3) B(1)-C(13)-C(14)-C(15) -178.4(2) F(1)-C(14)-C(15)-F(2) 1.3(3) C(13)-C(14)-C(15)-F(2) -178.76(19) F(1)-C(14)-C(15)-C(16) -178.42(19) C(13)-C(14)-C(15)-C(16) 1.5(3) F(2)-C(15)-C(16)-F(3) 0.0(3) C(14)-C(15)-C(16)-F(3) 179.73(19) F(2)-C(15)-C(16)-C(17) -178.5(2) C(14)-C(15)-C(16)-C(17) 1.2(3) F(3)-C(16)-C(17)-F(4) 0.8(3) C(15)-C(16)-C(17)-F(4) 179.3(2) F(3)-C(16)-C(17)-C(18) -179.9(2) C(15)-C(16)-C(17)-C(18) -1.3(3) F(4)-C(17)-C(18)-F(5) -1.3(3) C(16)-C(17)-C(18)-F(5) 179.42(19) F(4)-C(17)-C(18)-C(13) 178.1(2) C(16)-C(17)-C(18)-C(13) -1.2(4) C(14)-C(13)-C(18)-F(5) -177.09(18) B(1)-C(13)-C(18)-F(5) -1.9(3) C(14)-C(13)-C(18)-C(17) 3.6(3) B(1)-C(13)-C(18)-C(17) 178.8(2) C(24)-C(19)-C(20)-F(6) 179.34(18) B(1)-C(19)-C(20)-F(6) 5.1(3) C(24)-C(19)-C(20)-C(21) -1.4(3) 145

B(1)-C(19)-C(20)-C(21) -175.6(2) F(6)-C(20)-C(21)-F(7) 2.5(3) C(19)-C(20)-C(21)-F(7) -176.73(19) F(6)-C(20)-C(21)-C(22) 179.51(19) C(19)-C(20)-C(21)-C(22) 0.2(3) F(7)-C(21)-C(22)-F(8) -0.7(3) C(20)-C(21)-C(22)-F(8) -177.72(19) F(7)-C(21)-C(22)-C(23) 177.45(19) C(20)-C(21)-C(22)-C(23) 0.4(3) F(8)-C(22)-C(23)-F(9) -1.1(3) C(21)-C(22)-C(23)-F(9) -179.23(19) F(8)-C(22)-C(23)-C(24) 178.33(19) C(21)-C(22)-C(23)-C(24) 0.2(3) F(9)-C(23)-C(24)-F(10) -3.3(3) C(22)-C(23)-C(24)-F(10) 177.29(19) F(9)-C(23)-C(24)-C(19) 177.87(19) C(22)-C(23)-C(24)-C(19) -1.5(3) C(20)-C(19)-C(24)-F(10) -176.71(18) B(1)-C(19)-C(24)-F(10) -3.0(3) C(20)-C(19)-C(24)-C(23) 2.1(3) B(1)-C(19)-C(24)-C(23) 175.8(2) C(30)-C(25)-C(26)-F(11) -179.62(18) B(1)-C(25)-C(26)-F(11) -5.6(3) C(30)-C(25)-C(26)-C(27) 0.8(3) B(1)-C(25)-C(26)-C(27) 174.8(2) F(11)-C(26)-C(27)-F(12) -0.8(3) C(25)-C(26)-C(27)-F(12) 178.9(2) F(11)-C(26)-C(27)-C(28) 179.76(19) C(25)-C(26)-C(27)-C(28) -0.6(3) F(12)-C(27)-C(28)-F(13) 0.1(3) C(26)-C(27)-C(28)-F(13) 179.54(19) F(12)-C(27)-C(28)-C(29) -179.50(19) C(26)-C(27)-C(28)-C(29) 0.0(3) F(13)-C(28)-C(29)-F(14) 0.6(3) C(27)-C(28)-C(29)-F(14) -179.86(19) F(13)-C(28)-C(29)-C(30) -179.19(19) C(27)-C(28)-C(29)-C(30) 0.4(3) F(14)-C(29)-C(30)-F(15) -0.7(3) C(28)-C(29)-C(30)-F(15) 179.07(19) F(14)-C(29)-C(30)-C(25) -179.93(19) C(28)-C(29)-C(30)-C(25) -0.2(3) C(26)-C(25)-C(30)-F(15) -179.60(18) B(1)-C(25)-C(30)-F(15) 5.7(3) C(26)-C(25)-C(30)-C(29) -0.4(3) B(1)-C(25)-C(30)-C(29) -175.0(2) C(36)-C(31)-C(32)-F(16) -178.82(18) 146

B(1)-C(31)-C(32)-F(16) -0.8(3) C(36)-C(31)-C(32)-C(33) 3.1(3) B(1)-C(31)-C(32)-C(33) -178.9(2) F(16)-C(32)-C(33)-F(17) 1.1(3) C(31)-C(32)-C(33)-F(17) 179.24(19) F(16)-C(32)-C(33)-C(34) -177.87(19) C(31)-C(32)-C(33)-C(34) 0.3(3) F(17)-C(33)-C(34)-F(18) -0.9(3) C(32)-C(33)-C(34)-F(18) 178.06(19) F(17)-C(33)-C(34)-C(35) 178.24(19) C(32)-C(33)-C(34)-C(35) -2.8(3) F(18)-C(34)-C(35)-F(19) 0.8(3) C(33)-C(34)-C(35)-F(19) -178.3(2) F(18)-C(34)-C(35)-C(36) -179.14(19) C(33)-C(34)-C(35)-C(36) 1.7(3) F(19)-C(35)-C(36)-F(20) 2.3(3) C(34)-C(35)-C(36)-F(20) -177.78(19) F(19)-C(35)-C(36)-C(31) -177.91(19) C(34)-C(35)-C(36)-C(31) 2.0(3) C(32)-C(31)-C(36)-F(20) 175.54(18) B(1)-C(31)-C(36)-F(20) -2.3(3) C(32)-C(31)-C(36)-C(35) -4.2(3) B(1)-C(31)-C(36)-C(35) 178.0(2) C(42)-C(37)-C(38)-F(21) -174.72(19) B(2)-C(37)-C(38)-F(21) 2.1(3) C(42)-C(37)-C(38)-C(39) 4.2(3) B(2)-C(37)-C(38)-C(39) -179.0(2) F(21)-C(38)-C(39)-F(22) -3.3(3) C(37)-C(38)-C(39)-F(22) 177.7(2) F(21)-C(38)-C(39)-C(40) 176.93(19) C(37)-C(38)-C(39)-C(40) -2.0(4) F(22)-C(39)-C(40)-F(23) -0.1(3) C(38)-C(39)-C(40)-F(23) 179.68(19) F(22)-C(39)-C(40)-C(41) 178.9(2) C(38)-C(39)-C(40)-C(41) -1.4(3) F(23)-C(40)-C(41)-F(24) 0.1(3) C(39)-C(40)-C(41)-F(24) -178.8(2) F(23)-C(40)-C(41)-C(42) -178.83(19) C(39)-C(40)-C(41)-C(42) 2.2(3) F(24)-C(41)-C(42)-F(25) 0.3(3) C(40)-C(41)-C(42)-F(25) 179.23(19) F(24)-C(41)-C(42)-C(37) -178.7(2) C(40)-C(41)-C(42)-C(37) 0.2(3) C(38)-C(37)-C(42)-F(25) 177.76(18) B(2)-C(37)-C(42)-F(25) 0.6(3) C(38)-C(37)-C(42)-C(41) -3.2(3) 147

B(2)-C(37)-C(42)-C(41) 179.6(2) C(48)-C(43)-C(44)-F(26) -179.88(18) B(2)-C(43)-C(44)-F(26) -4.7(3) C(48)-C(43)-C(44)-C(45) 0.3(3) B(2)-C(43)-C(44)-C(45) 175.5(2) F(26)-C(44)-C(45)-F(27) -1.1(3) C(43)-C(44)-C(45)-F(27) 178.8(2) F(26)-C(44)-C(45)-C(46) 179.4(2) C(43)-C(44)-C(45)-C(46) -0.7(4) F(27)-C(45)-C(46)-F(28) -0.2(3) C(44)-C(45)-C(46)-F(28) 179.3(2) F(27)-C(45)-C(46)-C(47) -178.7(2) C(44)-C(45)-C(46)-C(47) 0.8(4) F(28)-C(46)-C(47)-F(29) -0.3(4) C(45)-C(46)-C(47)-F(29) 178.2(2) F(28)-C(46)-C(47)-C(48) -179.0(2) C(45)-C(46)-C(47)-C(48) -0.5(4) C(44)-C(43)-C(48)-F(30) 179.74(19) B(2)-C(43)-C(48)-F(30) 5.1(3) C(44)-C(43)-C(48)-C(47) 0.1(3) B(2)-C(43)-C(48)-C(47) -174.6(2) F(29)-C(47)-C(48)-F(30) 1.7(3) C(46)-C(47)-C(48)-F(30) -179.6(2) F(29)-C(47)-C(48)-C(43) -178.7(2) C(46)-C(47)-C(48)-C(43) 0.0(4) C(54)-C(49)-C(50)-F(31) 177.87(19) B(2)-C(49)-C(50)-F(31) 4.1(3) C(54)-C(49)-C(50)-C(51) -1.7(3) B(2)-C(49)-C(50)-C(51) -175.6(2) F(31)-C(50)-C(51)-F(32) 1.8(3) C(49)-C(50)-C(51)-F(32) -178.5(2) F(31)-C(50)-C(51)-C(52) -178.9(2) C(49)-C(50)-C(51)-C(52) 0.8(4) F(32)-C(51)-C(52)-F(33) -1.3(4) C(50)-C(51)-C(52)-F(33) 179.4(2) F(32)-C(51)-C(52)-C(53) 179.6(2) C(50)-C(51)-C(52)-C(53) 0.3(4) F(33)-C(52)-C(53)-F(34) -0.6(3) C(51)-C(52)-C(53)-F(34) 178.6(2) F(33)-C(52)-C(53)-C(54) -179.3(2) C(51)-C(52)-C(53)-C(54) -0.1(4) F(34)-C(53)-C(54)-F(35) -0.9(3) C(52)-C(53)-C(54)-F(35) 177.8(2) F(34)-C(53)-C(54)-C(49) -179.7(2) C(52)-C(53)-C(54)-C(49) -1.0(4) C(50)-C(49)-C(54)-F(35) -176.83(19) 148

B(2)-C(49)-C(54)-F(35) -3.6(3) C(50)-C(49)-C(54)-C(53) 1.9(3) B(2)-C(49)-C(54)-C(53) 175.1(2) C(60)-C(55)-C(56)-F(36) 175.43(18) B(2)-C(55)-C(56)-F(36) -1.8(3) C(60)-C(55)-C(56)-C(57) -3.3(3) B(2)-C(55)-C(56)-C(57) 179.5(2) F(36)-C(56)-C(57)-F(37) 2.3(3) C(55)-C(56)-C(57)-F(37) -178.87(19) F(36)-C(56)-C(57)-C(58) -176.52(18) C(55)-C(56)-C(57)-C(58) 2.3(3) F(37)-C(57)-C(58)-F(38) 1.6(3) C(56)-C(57)-C(58)-F(38) -179.57(19) F(37)-C(57)-C(58)-C(59) -178.80(19) C(56)-C(57)-C(58)-C(59) 0.1(3) F(38)-C(58)-C(59)-F(39) 0.6(3) C(57)-C(58)-C(59)-F(39) -179.01(19) F(38)-C(58)-C(59)-C(60) 178.6(2) C(57)-C(58)-C(59)-C(60) -1.0(3) F(39)-C(59)-C(60)-F(40) -0.8(3) C(58)-C(59)-C(60)-F(40) -178.76(19) F(39)-C(59)-C(60)-C(55) 177.7(2) C(58)-C(59)-C(60)-C(55) -0.2(3) C(56)-C(55)-C(60)-F(40) -179.24(18) B(2)-C(55)-C(60)-F(40) -1.7(3) C(56)-C(55)-C(60)-C(59) 2.3(3) B(2)-C(55)-C(60)-C(59) 179.8(2) C(24)-C(19)-B(1)-C(13) 126.3(2) C(20)-C(19)-B(1)-C(13) -60.3(3) C(24)-C(19)-B(1)-C(31) 9.5(3) C(20)-C(19)-B(1)-C(31) -177.17(18) C(24)-C(19)-B(1)-C(25) -111.3(2) C(20)-C(19)-B(1)-C(25) 62.1(2) C(14)-C(13)-B(1)-C(19) -10.1(3) C(18)-C(13)-B(1)-C(19) 175.49(19) C(14)-C(13)-B(1)-C(31) 112.3(2) C(18)-C(13)-B(1)-C(31) -62.1(2) C(14)-C(13)-B(1)-C(25) -125.2(2) C(18)-C(13)-B(1)-C(25) 60.4(3) C(36)-C(31)-B(1)-C(19) -122.3(2) C(32)-C(31)-B(1)-C(19) 60.0(3) C(36)-C(31)-B(1)-C(13) 115.1(2) C(32)-C(31)-B(1)-C(13) -62.6(2) C(36)-C(31)-B(1)-C(25) -8.2(3) C(32)-C(31)-B(1)-C(25) 174.12(18) C(26)-C(25)-B(1)-C(19) -115.3(2) 149

C(30)-C(25)-B(1)-C(19) 58.4(2) C(26)-C(25)-B(1)-C(13) 6.6(3) C(30)-C(25)-B(1)-C(13) -179.72(18) C(26)-C(25)-B(1)-C(31) 123.8(2) C(30)-C(25)-B(1)-C(31) -62.5(2) C(38)-C(37)-B(2)-C(55) 124.7(2) C(42)-C(37)-B(2)-C(55) -58.6(3) C(38)-C(37)-B(2)-C(43) 10.2(3) C(42)-C(37)-B(2)-C(43) -173.16(19) C(38)-C(37)-B(2)-C(49) -114.1(2) C(42)-C(37)-B(2)-C(49) 62.6(2) C(56)-C(55)-B(2)-C(37) -7.7(3) C(60)-C(55)-B(2)-C(37) 175.18(19) C(56)-C(55)-B(2)-C(43) 113.3(2) C(60)-C(55)-B(2)-C(43) -63.8(2) C(56)-C(55)-B(2)-C(49) -123.9(2) C(60)-C(55)-B(2)-C(49) 59.0(3) C(48)-C(43)-B(2)-C(37) -125.3(2) C(44)-C(43)-B(2)-C(37) 60.3(3) C(48)-C(43)-B(2)-C(55) 113.1(2) C(44)-C(43)-B(2)-C(55) -61.3(2) C(48)-C(43)-B(2)-C(49) -7.7(3) C(44)-C(43)-B(2)-C(49) 177.87(19) C(54)-C(49)-B(2)-C(37) -111.6(2) C(50)-C(49)-B(2)-C(37) 61.2(2) C(54)-C(49)-B(2)-C(55) 10.7(3) C(50)-C(49)-B(2)-C(55) -176.47(19) C(54)-C(49)-B(2)-C(43) 125.6(2) C(50)-C(49)-B(2)-C(43) -61.6(3) ______Symmetry transformations used to generate equivalent atoms:

150

+ - Appendix 4. Supplement Material for [P(NMe2)3Cl ][P3N3Cl5O ]

+ - [P(NMe2)3Cl ][P3N3Cl5O ]

151

+ - [P(NMe2)3Cl ][P3N3Cl5O ] (Disorder Major)

152

+ - [P(NMe2)3Cl ][P3N3Cl5O ] (Disorder Minor)

153

+ [P(NMe2)3Cl ] (Disorder Major)

154

- [P3N3Cl5O ] (Disorder Major)

155

+ [P(NMe2)3Cl ] (Disorder Minor)

156

- [P3N3Cl5O ] (Disorder Minor)

+ - Table 1.Crystal data and structure refinement for [P(NMe2)3Cl ][P3N3Cl5O ] Empirical formula C6H18Cl6N6OP4 Formula weight 526.84 Temperature 100(2) K Wavelength 0.71073 Å Crystal system Monoclinic Space group P2(1)/c Unit cell dimensions a = 8.392(2) Å α= 90° b = 21.563(6) Å β= 107.462(4)°

157

c = 12.185(3) Å γ = 90° Volume 2103.4(9) Å3 Z 4 Density (calculated) 1.664 Mg/m3 Absorption coefficient 1.129 mm-1 F(000) 1064 Crystal size 0.22 x 0.11 x 0.10 mm3 Theta range for data collection 1.89 to 26.30°. Index ranges -10<=h<=10, -26<=k<=26, -15<=l<=15 Reflections collected 16632 Independent reflections 4259 [R(int) = 0.0392] Completeness to theta = 26.30° 99.8 % Absorption correction Semi-empirical from equivalents Max. and min. transmission 0.8954 and 0.7892 Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 4259 / 0 / 310 Goodness-of-fit on F2 1.063 Final R indices [I>2sigma(I)] R1 = 0.0440, wR2 = 0.1070 R indices (all data) R1 = 0.0555, wR2 = 0.1147 Largest diff. peak and hole 0.638 and -0.565 e.Å-3

Table 2. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x 103) for C6H18Cl6N6OP4. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. ______x y z U(eq) ______Cl(1) 4895(1) 5884(1) 3997(1) 41(1) Cl(2) -567(1) 7038(1) 794(1) 48(1) Cl(5) 6436(1) 7597(1) 3152(1) 58(1) Cl(3A) 671(5) 6967(3) 3535(4) 39(1) Cl(4A) 5055(4) 7497(3) 390(4) 35(1) Cl(6A) 7198(3) 4280(1) 3913(2) 32(1) Cl(3B) 845(5) 7178(3) 3343(4) 37(1) Cl(4B) 4787(5) 7704(3) 683(5) 35(1) Cl(6B) 8931(4) 5355(1) 3555(2) 42(1) P(1) 3883(1) 5946(1) 2222(1) 28(1) P(2) 1548(1) 6875(1) 2085(1) 33(1) P(3) 4612(1) 7176(1) 1907(1) 38(1) P(4A) 8446(3) 4447(1) 2768(2) 24(1)

158

P(4B) 8845(3) 4608(1) 2541(2) 26(1) O(1) 3996(3) 5330(1) 1743(2) 45(1) N(1) 1985(3) 6176(1) 2054(2) 30(1) N(2) 2878(3) 7394(1) 2043(2) 45(1) N(3) 4992(3) 6474(1) 1855(2) 33(1) N(4) 10433(3) 4226(1) 3244(3) 52(1) N(5A) 7543(5) 4066(2) 1619(4) 27(1) N(6A) 8383(5) 5181(2) 2541(4) 28(1) N(5B) 8701(5) 4852(2) 1276(4) 28(1) N(6B) 7223(6) 4219(2) 2566(4) 28(1) C(1) 10681(4) 3599(2) 3746(4) 62(1) C(2) 11961(4) 4547(2) 3261(3) 57(1) C(3A) 8417(8) 3652(3) 1067(5) 43(2) C(4A) 5713(9) 4121(4) 1063(7) 35(2) C(5A) 8951(11) 5622(4) 3508(8) 29(2) C(6A) 7950(7) 5470(3) 1399(6) 29(1) C(3B) 9871(8) 4699(3) 631(5) 40(2) C(4B) 7479(9) 5336(3) 760(6) 36(1) C(5B) 6731(15) 4143(6) 3618(10) 38(3) C(6B) 6069(11) 3947(4) 1533(7) 40(2) ______

Table 3. Bond lengths [Å] and angles [°] for C6H18Cl6N6OP4. ______Cl(1)-P(1) 2.0777(11) P(4B)-N(5B) 1.599(5) Cl(2)-P(2) 2.0181(10) P(4B)-N(6B) 1.606(5) Cl(5)-P(3) 2.0190(11) N(4)-C(2) 1.452(4) Cl(3A)-P(2) 2.117(5) N(4)-C(1) 1.473(4) Cl(4A)-P(3) 2.110(4) N(5A)-C(3A) 1.444(7) Cl(6A)-P(4A) 2.013(4) N(5A)-C(4A) 1.486(8) Cl(3B)-P(2) 1.915(4) N(6A)-C(6A) 1.468(7) Cl(4B)-P(3) 1.917(3) N(6A)-C(5A) 1.478(9) Cl(6B)-P(4B) 2.020(3) N(5B)-C(4B) 1.466(8) P(1)-O(1) 1.464(2) N(5B)-C(3B) 1.468(7) P(1)-N(3) 1.617(2) N(6B)-C(6B) 1.461(9) P(1)-N(1) 1.622(2) N(6B)-C(5B) 1.469(13) P(2)-N(1) 1.554(2) C(1)-H(1A) 0.9800 P(2)-N(2) 1.591(3) C(1)-H(1B) 0.9800 P(3)-N(3) 1.551(3) C(1)-H(1C) 0.9800 P(3)-N(2) 1.585(3) C(2)-H(2A) 0.9800 P(4A)-N(5A) 1.604(5) C(2)-H(2B) 0.9800 P(4A)-N(6A) 1.604(5) C(2)-H(2C) 0.9800 P(4A)-N(4) 1.663(3) C(3A)-H(3A1) 0.9800 P(4B)-N(4) 1.582(3) C(3A)-H(3A2) 0.9800 159

C(3A)-H(3A3) 0.9800 N(5A)-P(4A)-N(6A) 111.9(3) C(4A)-H(4A1) 0.9800 N(5A)-P(4A)-N(4) 108.6(2) C(4A)-H(4A2) 0.9800 N(6A)-P(4A)-N(4) 108.7(2) C(4A)-H(4A3) 0.9800 N(5A)-P(4A)-Cl(6A) 107.8(2) C(5A)-H(5A1) 0.9800 N(6A)-P(4A)-Cl(6A) 107.4(2) C(5A)-H(5A2) 0.9800 N(4)-P(4A)-Cl(6A) 112.47(18) C(5A)-H(5A3) 0.9800 N(4)-P(4B)-N(5B) 120.1(2) C(6A)-H(6A1) 0.9800 N(4)-P(4B)-N(6B) 107.4(2) C(6A)-H(6A2) 0.9800 N(5B)-P(4B)-N(6B) 111.8(3) C(6A)-H(6A3) 0.9800 N(4)-P(4B)-Cl(6B) 102.39(18) C(3B)-H(3B1) 0.9800 N(5B)-P(4B)-Cl(6B) 107.7(2) C(3B)-H(3B2) 0.9800 N(6B)-P(4B)-Cl(6B) 106.2(2) C(3B)-H(3B3) 0.9800 P(2)-N(1)-P(1) 121.61(14) C(4B)-H(4B1) 0.9800 P(3)-N(2)-P(2) 117.98(15) C(4B)-H(4B2) 0.9800 P(3)-N(3)-P(1) 122.20(14) C(4B)-H(4B3) 0.9800 C(2)-N(4)-C(1) 114.7(3) C(5B)-H(5B1) 0.9800 C(2)-N(4)-P(4B) 110.9(2) C(5B)-H(5B2) 0.9800 C(1)-N(4)-P(4B) 133.9(2) C(5B)-H(5B3) 0.9800 C(2)-N(4)-P(4A) 131.0(2) C(6B)-H(6B1) 0.9800 C(1)-N(4)-P(4A) 114.2(2) C(6B)-H(6B2) 0.9800 C(3A)-N(5A)-C(4A) 115.9(5) C(6B)-H(6B3) 0.9800 C(3A)-N(5A)-P(4A) 123.4(4) O(1)-P(1)-N(3) 114.61(13) C(4A)-N(5A)-P(4A) 120.7(4) O(1)-P(1)-N(1) 113.96(12) C(6A)-N(6A)-C(5A) 114.3(5) N(3)-P(1)-N(1) 111.97(12) C(6A)-N(6A)-P(4A) 124.6(4) O(1)-P(1)-Cl(1) 107.58(10) C(5A)-N(6A)-P(4A) 120.7(4) N(3)-P(1)-Cl(1) 104.11(9) C(4B)-N(5B)-C(3B) 115.1(5) N(1)-P(1)-Cl(1) 103.34(9) C(4B)-N(5B)-P(4B) 119.3(4) N(1)-P(2)-N(2) 120.52(13) C(3B)-N(5B)-P(4B) 124.9(4) N(1)-P(2)-Cl(3B) 118.8(2) C(6B)-N(6B)-C(5B) 114.8(6) N(2)-P(2)-Cl(3B) 100.0(2) C(6B)-N(6B)-P(4B) 122.7(5) N(1)-P(2)-Cl(2) 107.93(9) C(5B)-N(6B)-P(4B) 122.4(5) N(2)-P(2)-Cl(2) 108.28(10) N(4)-C(1)-H(1A) 109.5 Cl(3B)-P(2)-Cl(2) 98.88(12) N(4)-C(1)-H(1B) 109.5 N(1)-P(2)-Cl(3A) 104.8(2) H(1A)-C(1)-H(1B) 109.5 N(2)-P(2)-Cl(3A) 112.6(2) N(4)-C(1)-H(1C) 109.5 Cl(2)-P(2)-Cl(3A) 100.93(11) H(1A)-C(1)-H(1C) 109.5 N(3)-P(3)-N(2) 120.06(13) H(1B)-C(1)-H(1C) 109.5 N(3)-P(3)-Cl(4B) 118.9(3) N(4)-C(2)-H(2A) 109.5 N(2)-P(3)-Cl(4B) 101.0(2) N(4)-C(2)-H(2B) 109.5 N(3)-P(3)-Cl(5) 110.54(10) H(2A)-C(2)-H(2B) 109.5 N(2)-P(3)-Cl(5) 107.50(11) N(4)-C(2)-H(2C) 109.5 Cl(4B)-P(3)-Cl(5) 95.71(13) H(2A)-C(2)-H(2C) 109.5 N(3)-P(3)-Cl(4A) 101.0(3) H(2B)-C(2)-H(2C) 109.5 N(2)-P(3)-Cl(4A) 113.75(19) N(5B)-C(3B)-H(3B1) 109.5 Cl(5)-P(3)-Cl(4A) 102.56(12) N(5B)-C(3B)-H(3B2) 109.5 160

H(3B1)-C(3B)-H(3B2) 109.5 H(5B1)-C(5B)-H(5B3) 109.5 N(5B)-C(3B)-H(3B3) 109.5 H(5B2)-C(5B)-H(5B3) 109.5 H(3B1)-C(3B)-H(3B3) 109.5 N(6B)-C(6B)-H(6B1) 109.5 H(3B2)-C(3B)-H(3B3) 109.5 N(6B)-C(6B)-H(6B2) 109.5 N(5B)-C(4B)-H(4B1) 109.5 H(6B1)-C(6B)-H(6B2) 109.5 N(5B)-C(4B)-H(4B2) 109.5 N(6B)-C(6B)-H(6B3) 109.5 H(4B1)-C(4B)-H(4B2) 109.5 H(6B1)-C(6B)-H(6B3) 109.5 N(5B)-C(4B)-H(4B3) 109.5 H(6B2)-C(6B)-H(6B3) 109.5 H(4B1)-C(4B)-H(4B3) 109.5 ______H(4B2)-C(4B)-H(4B3) 109.5 ___ N(6B)-C(5B)-H(5B1) 109.5 Symmetry transformations used to N(6B)-C(5B)-H(5B2) 109.5 generate equivalent atoms: H(5B1)-C(5B)-H(5B2) 109.5 N(6B)-C(5B)-H(5B3) 109.5

Table 4. Anisotropic displacement parameters (Å2x 103) for C6H18Cl6N6OP4. The anisotropic displacement factor exponent takes the form: -22[ h2 a*2U11 + ... + 2 h k a* b* U12 ] ______U11 U22 U33 U23 U13 U12 ______Cl(1) 34(1) 53(1) 33(1) 11(1) 6(1) 6(1) Cl(2) 36(1) 35(1) 55(1) 2(1) -16(1) 3(1) Cl(5) 39(1) 46(1) 67(1) -10(1) -18(1) -4(1) Cl(3A) 38(1) 44(2) 41(1) -5(1) 20(1) 0(1) Cl(4A) 34(1) 44(2) 26(1) 8(1) 11(1) 0(1) Cl(6A) 33(1) 34(1) 32(1) 0(1) 15(1) -6(1) Cl(3B) 35(1) 40(2) 40(1) 1(1) 20(1) 3(1) Cl(4B) 38(1) 37(2) 31(1) 4(1) 12(1) -2(1) Cl(6B) 60(1) 36(1) 33(1) -12(1) 15(1) -11(1) P(1) 26(1) 27(1) 31(1) -1(1) 9(1) 1(1) P(2) 27(1) 31(1) 34(1) -4(1) -1(1) 6(1) P(3) 32(1) 35(1) 36(1) 9(1) -5(1) -9(1) P(4A) 24(1) 25(1) 23(1) 1(1) 5(1) 0(1) P(4B) 25(1) 28(1) 22(1) -1(1) 4(1) -3(1) O(1) 35(1) 35(1) 64(2) -14(1) 14(1) 1(1) N(1) 24(1) 30(1) 35(1) 2(1) 9(1) 1(1) N(2) 33(1) 29(1) 61(2) -2(1) -6(1) 2(1) N(3) 29(1) 37(1) 35(1) 1(1) 12(1) -4(1) N(4) 33(1) 34(1) 70(2) 8(1) -13(1) -1(1) N(5A) 23(2) 27(2) 27(2) -4(2) 1(2) 2(2) N(6A) 28(2) 26(2) 27(2) -3(2) 5(2) -4(2) 161

N(5B) 26(2) 33(2) 25(2) -1(2) 8(2) 3(2) N(6B) 18(2) 35(3) 29(3) -1(2) 4(2) -6(2) C(1) 34(2) 30(2) 117(3) 8(2) 16(2) 2(1) C(2) 50(2) 58(2) 63(2) 20(2) 17(2) -3(2) C(3A) 41(3) 51(4) 32(3) -13(3) 1(3) 17(3) C(4A) 22(4) 39(4) 40(5) -6(3) 5(3) -2(3) C(5A) 30(3) 29(4) 24(3) -9(4) 1(2) -1(4) C(6A) 22(3) 33(3) 32(3) 4(3) 8(3) 2(2) C(3B) 37(3) 51(4) 32(3) -9(3) 12(3) -6(3) C(4B) 43(4) 30(3) 32(4) 4(3) 8(3) 9(3) C(5B) 42(7) 39(6) 41(7) -3(4) 22(5) -7(4) C(6B) 37(5) 40(5) 39(5) -6(3) 4(4) -9(4)

Table 5. Hydrogen coordinates ( x 104) and isotropic displacement parameters

(Å2x 10 3) for C6H18Cl6N6OP4. ______x y z U(eq) ______H(1A) 11237 3338 3313 93 H(1B) 9595 3418 3709 93 H(1C) 11375 3623 4551 93 H(2A) 12613 4634 4059 85 H(2B) 11682 4938 2837 85 H(2C) 12618 4287 2899 85 H(3A1) 7844 3250 930 65 H(3A2) 9565 3594 1564 65 H(3A3) 8436 3830 331 65 H(4A1) 5497 4244 257 52 H(4A2) 5255 4435 1466 52 H(4A3) 5179 3720 1099 52 H(5A1) 10057 5782 3540 44 H(5A2) 9015 5409 4231 44 H(5A3) 8158 5967 3395 44 H(6A1) 7070 5779 1332 43 H(6A2) 7550 5151 806 43 H(6A3) 8940 5673 1295 43 H(3B1) 9247 4626 -178 59 H(3B2) 10497 4324 956 59 H(3B3) 10649 5044 684 59 H(4B1) 8043 5739 844 54 H(4B2) 6613 5347 1149 54 H(4B3) 6965 5246 -59 54 162

H(5B1) 5710 4381 3548 58 H(5B2) 7629 4294 4280 58 H(5B3) 6525 3703 3727 58 H(6B1) 6147 3494 1582 60 H(6B2) 6361 4089 854 60 H(6B3) 4926 4076 1471 60

Table 6. Torsion angles [°] for C6H18Cl6N6OP4. ______N(2)-P(2)-N(1)-P(1) 11.9(2) Cl(3B)-P(2)-N(1)-P(1) -111.8(2) Cl(2)-P(2)-N(1)-P(1) 136.85(13) Cl(3A)-P(2)-N(1)-P(1) -116.20(17) O(1)-P(1)-N(1)-P(2) -157.65(16) N(3)-P(1)-N(1)-P(2) -25.5(2) Cl(1)-P(1)-N(1)-P(2) 85.92(16) N(3)-P(3)-N(2)-P(2) -1.7(3) Cl(4B)-P(3)-N(2)-P(2) 131.2(2) Cl(5)-P(3)-N(2)-P(2) -129.13(15) Cl(4A)-P(3)-N(2)-P(2) 118.0(3) N(1)-P(2)-N(2)-P(3) 2.9(3) Cl(3B)-P(2)-N(2)-P(3) 135.2(2) Cl(2)-P(2)-N(2)-P(3) -121.93(15) Cl(3A)-P(2)-N(2)-P(3) 127.4(2) N(2)-P(3)-N(3)-P(1) -14.4(2) Cl(4B)-P(3)-N(3)-P(1) -139.26(15) Cl(5)-P(3)-N(3)-P(1) 111.61(16) Cl(4A)-P(3)-N(3)-P(1) -140.35(16) O(1)-P(1)-N(3)-P(3) 158.74(16) N(1)-P(1)-N(3)-P(3) 26.9(2) Cl(1)-P(1)-N(3)-P(3) -84.02(17) N(5B)-P(4B)-N(4)-C(2) 50.8(4) N(6B)-P(4B)-N(4)-C(2) 179.9(3) Cl(6B)-P(4B)-N(4)-C(2) -68.4(3) N(5B)-P(4B)-N(4)-C(1) -120.5(4) N(6B)-P(4B)-N(4)-C(1) 8.7(5) Cl(6B)-P(4B)-N(4)-C(1) 120.3(4) N(5B)-P(4B)-N(4)-P(4A) -145.5(5) N(6B)-P(4B)-N(4)-P(4A) -16.4(3) Cl(6B)-P(4B)-N(4)-P(4A) 95.3(4) N(5A)-P(4A)-N(4)-C(2) 108.9(4) N(6A)-P(4A)-N(4)-C(2) -13.1(4) Cl(6A)-P(4A)-N(4)-C(2) -131.9(3) N(5A)-P(4A)-N(4)-C(1) -71.9(4)

163

N(6A)-P(4A)-N(4)-C(1) 166.1(3) Cl(6A)-P(4A)-N(4)-C(1) 47.3(3) N(5A)-P(4A)-N(4)-P(4B) 88.5(4) N(6A)-P(4A)-N(4)-P(4B) -33.4(4) Cl(6A)-P(4A)-N(4)-P(4B) -152.2(5) N(6A)-P(4A)-N(5A)-C(3A) 114.4(5) N(4)-P(4A)-N(5A)-C(3A) -5.6(5) Cl(6A)-P(4A)-N(5A)-C(3A) -127.7(5) N(6A)-P(4A)-N(5A)-C(4A) -66.1(5) N(4)-P(4A)-N(5A)-C(4A) 173.9(5) Cl(6A)-P(4A)-N(5A)-C(4A) 51.7(5) N(5A)-P(4A)-N(6A)-C(6A) -14.5(5) N(4)-P(4A)-N(6A)-C(6A) 105.5(4) Cl(6A)-P(4A)-N(6A)-C(6A) -132.6(4) N(5A)-P(4A)-N(6A)-C(5A) 172.3(5) N(4)-P(4A)-N(6A)-C(5A) -67.8(5) Cl(6A)-P(4A)-N(6A)-C(5A) 54.2(5) N(4)-P(4B)-N(5B)-C(4B) -163.8(4) N(6B)-P(4B)-N(5B)-C(4B) 69.1(5) Cl(6B)-P(4B)-N(5B)-C(4B) -47.3(5) N(4)-P(4B)-N(5B)-C(3B) 6.6(6) N(6B)-P(4B)-N(5B)-C(3B) -120.6(5) Cl(6B)-P(4B)-N(5B)-C(3B) 123.1(4) N(4)-P(4B)-N(6B)-C(6B) -114.2(5) N(5B)-P(4B)-N(6B)-C(6B) 19.6(6) Cl(6B)-P(4B)-N(6B)-C(6B) 136.8(5) N(4)-P(4B)-N(6B)-C(5B) 69.7(7) N(5B)-P(4B)-N(6B)-C(5B) -156.6(7) Cl(6B)-P(4B)-N(6B)-C(5B) -39.3(7) ______Symmetry transformations used to generate equivalent atoms:

164

+ - Appendix 5. Supplement material for [P(NMe2)3Cl ][P4N4Cl7O ]

+ - [P(NMe2)3Cl ][P4N4Cl7O ]

165

+ [P(NMe2)3Cl ]

166

- [P4N4Cl7O ] (Disorder Major)

167

- [P4N4Cl7O ] (Disorder Minor)

+ - Table 1. Crystal data and structure refinement for [P(NMe2)3Cl ][P4N4Cl7O ]. Empirical formula C6H18Cl8N7OP5 Formula weight 642.72 Temperature 100(2) K 168

Wavelength 0.71073 Å Crystal system Monoclinic Space group P2(1)/c Unit cell dimensions a = 10.818(3) Å = 90° b = 10.114(3) Å = 99.408(6)° c = 22.474(7) Å  = 90° Volume 2425.8(13) Å3 Z 4 Density (calculated) 1.760 Mg/m3 Absorption coefficient 1.274 mm-1 F(000) 1288 Crystal size 0.15 x 0.06 x 0.05 mm3 Theta range for data collection 1.84 to 26.30°. Index ranges -13<=h<=13, -12<=k<=12, -27<=l<=27 Reflections collected 18855 Independent reflections 4930 [R(int) = 0.0610] Completeness to theta = 26.30° 100.0 % Absorption correction Semi-empirical from equivalents Max. and min. transmission 0.9391 and 0.8319 Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 4930 / 0 / 270 Goodness-of-fit on F2 1.029 Final R indices [I>2sigma(I)] R1 = 0.0545, wR2 = 0.1183 R indices (all data) R1 = 0.0780, wR2 = 0.1289 Largest diff. peak and hole 1.217 and -0.744 e.Å-3

Table 2. Atomic coordinates ( x 104) and equivalent isotropic displacement + - parameters (Å2x 103) for [P(NMe2)3Cl ][P4N4Cl7O ]. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. ______x y z U(eq) ______Cl(1) -197(1) 1868(1) 5662(1) 35(1) Cl(2) 2025(1) -1124(1) 5791(1) 42(1) Cl(3) 3599(1) -815(1) 7077(1) 41(1) Cl(4) 6033(1) 1628(1) 5460(1) 51(1) Cl(5) 6297(1) 1560(2) 6845(1) 63(1) Cl(6A) 3260(20) 5490(30) 5292(5) 40(3) Cl(6B) 3629(18) 5068(19) 5279(2) 42(3) Cl(7) 3396(1) 5408(1) 6644(1) 56(1) 169

Cl(8) 1787(1) 1378(1) 4500(1) 38(1) P(1) 1280(1) 2559(1) 6271(1) 27(1) P(2) 2918(1) 268(1) 6342(1) 30(1) P(3) 5004(1) 1849(1) 6107(1) 38(1) P(4) 3340(1) 4058(1) 5978(1) 32(1) P(5) 1714(1) 2519(1) 3763(1) 27(1) O(1) 777(3) 3347(3) 6726(1) 35(1) N(1) 2000(3) 1257(3) 6559(2) 31(1) N(2) 4042(3) 680(4) 6021(2) 36(1) N(3A) 4646(9) 3287(13) 6244(16) 41(5) N(3B) 4530(20) 3379(19) 5910(40) 48(10) N(4) 2072(3) 3347(3) 5834(2) 29(1) N(5) 1485(3) 3998(3) 3976(2) 31(1) N(6) 3047(3) 2362(4) 3546(2) 32(1) N(7) 612(3) 1967(4) 3259(2) 30(1) C(1) 508(4) 4303(4) 4347(2) 36(1) C(2) 2003(4) 5150(4) 3699(2) 39(1) C(3) 4208(4) 2467(5) 3986(2) 44(1) C(4) 3207(4) 2229(5) 2913(2) 40(1) C(5) 587(4) 578(4) 3076(2) 35(1) C(6) -406(4) 2793(5) 2941(2) 38(1)

Table 3. Bond lengths [Å] and P(4)-N(3B) 1.49(2) angles [°] for P(4)-N(4) 1.536(4) + - [P(NMe2)3Cl ][P4N4Cl7O ]. P(4)-N(3A) 1.638(19) ______P(5)-N(5) 1.603(4) ______P(5)-N(7) 1.604(4) Cl(1)-P(1) 2.0495(16) P(5)-N(6) 1.605(4) Cl(2)-P(2) 2.0149(17) N(5)-C(2) 1.475(6) Cl(3)-P(2) 2.0187(17) N(5)-C(1) 1.481(5) Cl(4)-P(3) 1.9830(19) N(6)-C(4) 1.466(5) Cl(5)-P(3) 2.008(2) N(6)-C(3) 1.469(5) Cl(6A)-P(4) 2.105(13) N(7)-C(5) 1.463(5) Cl(6B)-P(4) 1.942(8) N(7)-C(6) 1.471(5) Cl(7)-P(4) 2.0189(18) C(1)-H(1A) 0.9800 Cl(8)-P(5) 2.0094(16) C(1)-H(1B) 0.9800 P(1)-O(1) 1.469(3) C(1)-H(1C) 0.9800 P(1)-N(1) 1.611(4) C(2)-H(2A) 0.9800 P(1)-N(4) 1.615(4) C(2)-H(2B) 0.9800 P(2)-N(1) 1.543(4) C(2)-H(2C) 0.9800 P(2)-N(2) 1.568(4) C(3)-H(3A) 0.9800 P(3)-N(3A) 1.549(9) C(3)-H(3B) 0.9800 P(3)-N(2) 1.566(4) C(3)-H(3C) 0.9800 P(3)-N(3B) 1.67(3) C(4)-H(4A) 0.9800

170

C(4)-H(4B) 0.9800 N(5)-P(5)-N(6) 111.95(19) C(4)-H(4C) 0.9800 N(7)-P(5)-N(6) 110.61(18) C(5)-H(5A) 0.9800 N(5)-P(5)-Cl(8) 106.04(14) C(5)-H(5B) 0.9800 N(7)-P(5)-Cl(8) 107.86(14) C(5)-H(5C) 0.9800 N(6)-P(5)-Cl(8) 106.19(14) C(6)-H(6A) 0.9800 P(2)-N(1)-P(1) 134.1(2) C(6)-H(6B) 0.9800 P(3)-N(2)-P(2) 133.9(3) C(6)-H(6C) 0.9800 P(3)-N(3A)-P(4) 127.2(12) O(1)-P(1)-N(1) 111.93(18) P(4)-N(3B)-P(3) 130(2) O(1)-P(1)-N(4) 116.68(19) P(4)-N(4)-P(1) 130.3(2) N(1)-P(1)-N(4) 112.24(19) C(2)-N(5)-C(1) 115.4(3) O(1)-P(1)-Cl(1) 108.22(14) C(2)-N(5)-P(5) 121.5(3) N(1)-P(1)-Cl(1) 105.23(15) C(1)-N(5)-P(5) 121.5(3) N(4)-P(1)-Cl(1) 101.24(14) C(4)-N(6)-C(3) 115.9(4) N(1)-P(2)-N(2) 124.1(2) C(4)-N(6)-P(5) 124.0(3) N(1)-P(2)-Cl(2) 112.25(16) C(3)-N(6)-P(5) 119.9(3) N(2)-P(2)-Cl(2) 103.49(16) C(5)-N(7)-C(6) 115.5(3) N(1)-P(2)-Cl(3) 105.09(15) C(5)-N(7)-P(5) 120.7(3) N(2)-P(2)-Cl(3) 108.27(16) C(6)-N(7)-P(5) 123.8(3) Cl(2)-P(2)-Cl(3) 101.40(7) N(5)-C(1)-H(1A) 109.5 N(3A)-P(3)-N(2) 123.4(4) N(5)-C(1)-H(1B) 109.5 N(3A)-P(3)-N(3B) 26.3(14) H(1A)-C(1)-H(1B) 109.5 N(2)-P(3)-N(3B) 119.8(11) N(5)-C(1)-H(1C) 109.5 N(3A)-P(3)-Cl(4) 116.1(11) H(1A)-C(1)-H(1C) 109.5 N(2)-P(3)-Cl(4) 105.39(16) H(1B)-C(1)-H(1C) 109.5 N(3B)-P(3)-Cl(4) 96(2) N(5)-C(2)-H(2A) 109.5 N(3A)-P(3)-Cl(5) 97.8(11) N(5)-C(2)-H(2B) 109.5 N(2)-P(3)-Cl(5) 110.56(17) H(2A)-C(2)-H(2B) 109.5 N(3B)-P(3)-Cl(5) 120(2) N(5)-C(2)-H(2C) 109.5 Cl(4)-P(3)-Cl(5) 101.00(8) H(2A)-C(2)-H(2C) 109.5 N(3B)-P(4)-N(4) 121.3(13) H(2B)-C(2)-H(2C) 109.5 N(3B)-P(4)-N(3A) 26.9(19) N(6)-C(3)-H(3A) 109.5 N(4)-P(4)-N(3A) 122.8(4) N(6)-C(3)-H(3B) 109.5 N(3B)-P(4)-Cl(6B) 85(2) H(3A)-C(3)-H(3B) 109.5 N(4)-P(4)-Cl(6B) 109.3(4) N(6)-C(3)-H(3C) 109.5 N(3A)-P(4)-Cl(6B) 107.6(13) H(3A)-C(3)-H(3C) 109.5 N(3B)-P(4)-Cl(7) 118(3) H(3B)-C(3)-H(3C) 109.5 N(4)-P(4)-Cl(7) 112.97(15) N(6)-C(4)-H(4A) 109.5 N(3A)-P(4)-Cl(7) 97.6(8) N(6)-C(4)-H(4B) 109.5 Cl(6B)-P(4)-Cl(7) 104.8(5) H(4A)-C(4)-H(4B) 109.5 N(3B)-P(4)-Cl(6A) 100(2) N(6)-C(4)-H(4C) 109.5 N(4)-P(4)-Cl(6A) 103.8(3) H(4A)-C(4)-H(4C) 109.5 N(3A)-P(4)-Cl(6A) 121.5(13) H(4B)-C(4)-H(4C) 109.5 Cl(6B)-P(4)-Cl(6A) 16.0(2) N(7)-C(5)-H(5A) 109.5 Cl(7)-P(4)-Cl(6A) 94.1(8) N(7)-C(5)-H(5B) 109.5 N(5)-P(5)-N(7) 113.71(19) H(5A)-C(5)-H(5B) 109.5 171

N(7)-C(5)-H(5C) 109.5 N(7)-C(6)-H(6B) 109.5 H(5A)-C(5)-H(5C) 109.5 H(6A)-C(6)-H(6B) 109.5 H(5B)-C(5)-H(5C) 109.5 N(7)-C(6)-H(6C) 109.5 N(7)-C(6)-H(6A) 109.5 H(6A)-C(6)-H(6C) 109.5 to generate equivalent atoms: H(6B)-C(6)-H(6C) 109.5 Symmetry transformations used

Table 4. Anisotropic displacement parameters (Å2x 103) for + - [P(NMe2)3Cl ][P4N4Cl7O ]. The anisotropic displacement factor exponent takes the form: -22[ h2 a*2U11 + ... + 2 h k a* b* U12 ] ______U11 U22 U33 U23 U13 U12 ______Cl(1) 31(1) 38(1) 34(1) 3(1) 3(1) -6(1) Cl(2) 44(1) 36(1) 47(1) -5(1) 8(1) -10(1) Cl(3) 36(1) 36(1) 49(1) 10(1) 5(1) 6(1) Cl(4) 43(1) 68(1) 46(1) 8(1) 15(1) -14(1) Cl(5) 67(1) 78(1) 43(1) -4(1) 3(1) -20(1) Cl(6A) 40(5) 38(5) 38(2) 9(3) -1(2) -6(5) Cl(6B) 50(4) 43(4) 34(1) 4(2) 7(2) -17(4) Cl(7) 66(1) 62(1) 42(1) -21(1) 14(1) -25(1) Cl(8) 52(1) 32(1) 30(1) 5(1) 6(1) 3(1) P(1) 26(1) 30(1) 27(1) 1(1) 5(1) 2(1) P(2) 27(1) 26(1) 38(1) 3(1) 8(1) 0(1) P(3) 27(1) 30(1) 59(1) 1(1) 13(1) 1(1) P(4) 31(1) 24(1) 41(1) -3(1) 8(1) -2(1) P(5) 29(1) 26(1) 27(1) 0(1) 5(1) 2(1) O(1) 34(2) 39(2) 31(2) 3(1) 6(1) 10(1) N(1) 28(2) 32(2) 34(2) 6(2) 10(2) 5(2) N(2) 35(2) 26(2) 50(2) 0(2) 17(2) -3(2) N(3A) 28(4) 28(4) 63(13) 2(5) -8(5) -3(3) N(3B) 17(7) 51(10) 70(30) 26(10) -3(10) -4(6) N(4) 32(2) 26(2) 29(2) -3(2) 6(2) -2(2) N(5) 29(2) 29(2) 34(2) 2(2) 6(2) 2(2) N(6) 27(2) 36(2) 31(2) -6(2) 2(2) 3(2) N(7) 27(2) 32(2) 30(2) -1(2) 3(2) 0(2) C(1) 42(3) 31(2) 38(3) -1(2) 15(2) 9(2) C(2) 43(3) 30(2) 45(3) 8(2) 9(2) 5(2) C(3) 29(3) 57(3) 43(3) -9(2) -4(2) 1(2) C(4) 28(2) 59(3) 35(3) -4(2) 11(2) -2(2) C(5) 38(3) 32(2) 34(2) -6(2) 4(2) -8(2) C(6) 32(3) 45(3) 34(2) 5(2) 2(2) 2(2) 172

______

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Table 5. Hydrogen coordinates ( x 104) and isotropic displacement parameters + - (Å2x 10 3) for [P(NMe2)3Cl ][P4N4Cl7O ]. ______x y z U(eq) ______

H(1A) 806 5009 4634 54 H(1B) 330 3509 4569 54 H(1C) -258 4592 4085 54 H(2A) 1333 5590 3423 59 H(2B) 2657 4855 3474 59 H(2C) 2364 5771 4015 59 H(3A) 4634 1609 4024 66 H(3B) 4005 2731 4378 66 H(3C) 4758 3131 3848 66 H(4A) 3692 2980 2800 61 H(4B) 2383 2214 2656 61 H(4C) 3653 1405 2860 61 H(5A) -235 198 3103 53 H(5B) 1238 90 3343 53 H(5C) 742 515 2659 53 H(6A) -373 2788 2508 56 H(6B) -308 3702 3094 56 H(6C) -1214 2441 3010 56

+ - Table 6. Torsion angles [°] for [P(NMe2)3Cl ][P4N4Cl7O ]. ______N(2)-P(2)-N(1)-P(1) 43.4(4) Cl(2)-P(2)-N(1)-P(1) -82.1(3) Cl(3)-P(2)-N(1)-P(1) 168.5(3) O(1)-P(1)-N(1)-P(2) -164.7(3) N(4)-P(1)-N(1)-P(2) -31.2(4) Cl(1)-P(1)-N(1)-P(2) 78.0(3) N(3A)-P(3)-N(2)-P(2) -39.9(17) N(3B)-P(3)-N(2)-P(2) -71(3) Cl(4)-P(3)-N(2)-P(2) -176.6(3) Cl(5)-P(3)-N(2)-P(2) 75.0(4) N(1)-P(2)-N(2)-P(3) 38.3(5) Cl(2)-P(2)-N(2)-P(3) 167.6(3) Cl(3)-P(2)-N(2)-P(3) -85.4(3) N(2)-P(3)-N(3A)-P(4) -37(3) N(3B)-P(3)-N(3A)-P(4) 54(2) Cl(4)-P(3)-N(3A)-P(4) 96.0(19) Cl(5)-P(3)-N(3A)-P(4) -158(2) 174

N(3B)-P(4)-N(3A)-P(3) -63(2) N(4)-P(4)-N(3A)-P(3) 33(3) Cl(6B)-P(4)-N(3A)-P(3) -95(2) Cl(7)-P(4)-N(3A)-P(3) 156(2) Cl(6A)-P(4)-N(3A)-P(3) -104(2) N(4)-P(4)-N(3B)-P(3) -43(7) N(3A)-P(4)-N(3B)-P(3) 59(4) Cl(6B)-P(4)-N(3B)-P(3) -152(6) Cl(7)-P(4)-N(3B)-P(3) 104(5) Cl(6A)-P(4)-N(3B)-P(3) -156(5) N(3A)-P(3)-N(3B)-P(4) -67(5) N(2)-P(3)-N(3B)-P(4) 38(7) Cl(4)-P(3)-N(3B)-P(4) 150(6) Cl(5)-P(3)-N(3B)-P(4) -104(5) N(3B)-P(4)-N(4)-P(1) 94(3) N(3A)-P(4)-N(4)-P(1) 62.6(14) Cl(6B)-P(4)-N(4)-P(1) -170.1(8) Cl(7)-P(4)-N(4)-P(1) -53.8(3) Cl(6A)-P(4)-N(4)-P(1) -154.4(10) O(1)-P(1)-N(4)-P(4) 66.5(3) N(1)-P(1)-N(4)-P(4) -64.5(3) Cl(1)-P(1)-N(4)-P(4) -176.3(3) N(7)-P(5)-N(5)-C(2) -94.1(4) N(6)-P(5)-N(5)-C(2) 32.1(4) Cl(8)-P(5)-N(5)-C(2) 147.5(3) N(7)-P(5)-N(5)-C(1) 70.8(4) N(6)-P(5)-N(5)-C(1) -162.9(3) Cl(8)-P(5)-N(5)-C(1) -47.5(3) N(5)-P(5)-N(6)-C(4) -106.3(4) N(7)-P(5)-N(6)-C(4) 21.7(4) Cl(8)-P(5)-N(6)-C(4) 138.4(3) N(5)-P(5)-N(6)-C(3) 68.2(4) N(7)-P(5)-N(6)-C(3) -163.8(3) Cl(8)-P(5)-N(6)-C(3) -47.1(4) N(5)-P(5)-N(7)-C(5) -171.5(3) N(6)-P(5)-N(7)-C(5) 61.5(4) Cl(8)-P(5)-N(7)-C(5) -54.2(3) N(5)-P(5)-N(7)-C(6) 10.2(4) N(6)-P(5)-N(7)-C(6) -116.8(3) Cl(8)-P(5)-N(7)-C(6) 127.5(3) ______Symmetry transformations used to generate equivalent atoms:

175

- - Appendix 6. Supplement Material for [P(NMe2)3Cl ]Cl

- - [P(NMe2)3Cl ]Cl

- - Table 1. Crystal data and structure refinement for [P(NMe2)3Cl ]Cl . Empirical formula C6H18Cl2N3P Formula weight 234.10 Temperature 100(2) K Wavelength 0.71073 Å Crystal system Monoclinic Space group P2(1)/n Unit cell dimensions a = 8.008(3) Å = 90°. b = 10.588(5) Å = 92.623(6)°. c = 14.175(6) Å  = 90°. Volume 1200.7(9) Å3 Z 4 Density (calculated) 1.295 Mg/m3 Absorption coefficient 0.635 mm-1 F(000) 496 Crystal size 0.19 x 0.13 x 0.04 mm3 Theta range for data collection 2.40 to 26.29°. Index ranges -9<=h<=9, -12<=k<=13, -17<=l<=17 Reflections collected 9206

176

Independent reflections 2429 [R(int) = 0.0669] Completeness to theta = 26.29° 100.0 % Absorption correction Semi-empirical from equivalents Max. and min. transmission 0.9751 and 0.8889 Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 2429 / 0 / 115 Goodness-of-fit on F2 1.052 Final R indices [I>2sigma(I)] R1 = 0.0506, wR2 = 0.1265 R indices (all data) R1 = 0.0647, wR2 = 0.1387 Largest diff. peak and hole 0.938 and -0.367 e.Å-3

Table 2. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x 103) for C6H18Cl2N3P. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. ______x y z U(eq) ______Cl(1) 2288(1) 5014(1) 5609(1) 29(1) Cl(2) 2786(1) 5222(1) 1803(1) 28(1) P(1) 2274(1) 6956(1) 5632(1) 19(1) N(1) 1206(3) 7392(2) 4704(2) 22(1) N(2) 4182(3) 7398(3) 5628(2) 25(1) N(3) 1450(3) 7326(3) 6600(2) 24(1) C(1) 1610(4) 6907(3) 3766(2) 25(1) C(2) -261(4) 8219(3) 4718(2) 26(1) C(3) 4886(4) 8167(3) 4879(2) 30(1) C(4) 5419(4) 6834(3) 6310(2) 31(1) C(5) -54(4) 6686(3) 6933(2) 32(1) C(6) 2079(4) 8365(4) 7212(2) 36(1)

Table 3. Bond lengths [Å] and angles [°] for C6H18Cl2N3P. ______Cl(1)-P(1) 2.0568(14) C(1)-H(1A) 0.9600 P(1)-N(2) 1.598(3) C(1)-H(1B) 0.9600 P(1)-N(3) 1.598(3) C(1)-H(1C) 0.9600 P(1)-N(1) 1.604(3) C(2)-H(2A) 0.9600 N(1)-C(2) 1.466(4) C(2)-H(2B) 0.9600 N(1)-C(1) 1.475(4) C(2)-H(2C) 0.9600 N(2)-C(3) 1.470(4) C(3)-H(3A) 0.9600 N(2)-C(4) 1.479(4) C(3)-H(3B) 0.9600 N(3)-C(6) 1.475(4) C(3)-H(3C) 0.9600 N(3)-C(5) 1.478(4) C(4)-H(4A) 0.9600 177

C(4)-H(4B) 0.9600 N(1)-C(2)-H(2A) 109.5 C(4)-H(4C) 0.9600 N(1)-C(2)-H(2B) 109.5 C(5)-H(5A) 0.9600 H(2A)-C(2)-H(2B) 109.5 C(5)-H(5B) 0.9600 N(1)-C(2)-H(2C) 109.5 C(5)-H(5C) 0.9600 H(2A)-C(2)-H(2C) 109.5 C(6)-H(6A) 0.9600 H(2B)-C(2)-H(2C) 109.5 C(6)-H(6B) 0.9600 N(2)-C(3)-H(3A) 109.5 C(6)-H(6C) 0.9600 N(2)-C(3)-H(3B) 109.5 H(3A)-C(3)-H(3B) 109.5 N(2)-P(1)-N(3) 111.36(14) N(2)-C(3)-H(3C) 109.5 N(2)-P(1)-N(1) 112.75(14) H(3A)-C(3)-H(3C) 109.5 N(3)-P(1)-N(1) 114.10(14) H(3B)-C(3)-H(3C) 109.5 N(2)-P(1)-Cl(1) 106.66(11) N(2)-C(4)-H(4A) 109.5 N(3)-P(1)-Cl(1) 105.11(11) N(2)-C(4)-H(4B) 109.5 N(1)-P(1)-Cl(1) 106.12(10) H(4A)-C(4)-H(4B) 109.5 C(2)-N(1)-C(1) 115.5(2) N(2)-C(4)-H(4C) 109.5 C(2)-N(1)-P(1) 123.9(2) H(4A)-C(4)-H(4C) 109.5 C(1)-N(1)-P(1) 120.6(2) H(4B)-C(4)-H(4C) 109.5 C(3)-N(2)-C(4) 115.4(3) N(3)-C(5)-H(5A) 109.5 C(3)-N(2)-P(1) 124.3(2) N(3)-C(5)-H(5B) 109.5 C(4)-N(2)-P(1) 119.4(2) H(5A)-C(5)-H(5B) 109.5 C(6)-N(3)-C(5) 114.6(3) N(3)-C(5)-H(5C) 109.5 C(6)-N(3)-P(1) 122.9(2) H(5A)-C(5)-H(5C) 109.5 C(5)-N(3)-P(1) 122.4(2) H(5B)-C(5)-H(5C) 109.5 N(1)-C(1)-H(1A) 109.5 N(3)-C(6)-H(6A) 109.5 N(1)-C(1)-H(1B) 109.5 N(3)-C(6)-H(6B) 109.5 H(1A)-C(1)-H(1B) 109.5 H(6A)-C(6)-H(6B) 109.5 N(1)-C(1)-H(1C) 109.5 N(3)-C(6)-H(6C) 109.5 H(1A)-C(1)-H(1C) 109.5 H(6A)-C(6)-H(6C) 109.5 H(1B)-C(1)-H(1C) 109.5 H(6B)-C(6)-H(6C) 109.5 ______Symmetry transformations used to generate equivalent atoms:

Table 4. Anisotropic displacement parameters (Å2x 103) for C6H18Cl2N3P. The anisotropic displacement factor exponent takes the form: -22[ h2 a*2U11 + ... + 2 h k a* b* U12 ] ______U11 U22 U33 U23 U13 U12 ______Cl(1) 37(1) 25(1) 25(1) 1(1) 1(1) 0(1) Cl(2) 31(1) 30(1) 22(1) -2(1) 5(1) -2(1) P(1) 18(1) 26(1) 12(1) 0(1) 1(1) 0(1) N(1) 20(1) 31(2) 13(1) -2(1) 2(1) 3(1) N(2) 20(1) 35(2) 20(1) 3(1) 0(1) -1(1) 178

N(3) 23(1) 35(2) 15(1) -3(1) 3(1) -1(1) C(1) 28(2) 34(2) 12(1) -3(1) 2(1) 0(1) C(2) 22(2) 32(2) 23(2) 0(1) 3(1) 4(1) C(3) 22(2) 41(2) 29(2) 4(2) 4(1) -5(1) C(4) 22(2) 44(2) 26(2) 3(2) -8(1) 3(1) C(5) 28(2) 42(2) 27(2) 4(2) 13(1) 0(2) C(6) 35(2) 50(2) 22(2) -19(2) -4(1) -1(2)

Table 5. Hydrogen coordinates ( x 104) and isotropic displacement parameters

(Å2x 10 3) for C6H18Cl2N3P. ______x y z U(eq) ______

H(1A) 683 6426 3505 37 H(1B) 2582 6377 3826 37 H(1C) 1829 7602 3355 37 H(2A) -114 8921 4302 38 H(2B) -388 8524 5349 38 H(2C) -1240 7753 4514 38 H(3A) 5644 8778 5157 46 H(3B) 3998 8594 4530 46 H(3C) 5474 7630 4460 46 H(4A) 6074 6219 5994 47 H(4B) 4847 6434 6810 47 H(4C) 6139 7484 6569 47 H(5A) 223 6252 7514 48 H(5B) -454 6088 6466 48 H(5C) -908 7301 7035 48 H(6A) 1211 8980 7277 54 H(6B) 3020 8756 6934 54 H(6C) 2416 8036 7822 54 ______

179