Phosphorus-Containing Conjugated Polymers And

Home , Alan MacDiarmid

PHOSPHORUS-CONTAINING CONJUGATED POLYMERS AND

BIFUNCTIONAL ELECTROLYTES

MICHAEL FRANCIS RECTENWALD

Submitted to in partial fulfillment of the requirements for the degree of

Doctor of Philosophy

Thesis adviser: Professor John Protasiewicz

Department of Chemistry

CASE WESTERN RESERVE UNIVERSITY

May 2014 CASE WESTERN RESERVE UNIVERSITY

SCHOOL OF GRADUATE STUDIES

We hereby approve the thesis/dissertation of

Michael F. Rectenwald

candidate for the degree of Doctor of Philosophy*.

Committee Chair

Dr. Thomas Gray

Committee Member

Dr. Malcolm Kenney

Committee Member

Dr. Daniel Scherson

Committee Member

Dr. Stuart Rowan

Date of Defense

March 27, 2014

*We also certify that written approval has been obtained

for any proprietary material contained therein.

To Mom and Dad

To Tom and Mary

To Dave, Tom, Alex, and Mary K.

But most of all, to Elise

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Table of Contents

Dedication……………………………………………………………………………… ..ii

Table of Contents ………………………………………………………………………..iii

List of Charts …………………………………………………………………………….vi

List of Tables ……………………………………………………………………...…….vii

List of Figures ……………………………………………………………………………ix

List of Schemes ………………………………………………………………………....xvi

List of Abbreviations and Symbols …………………………………………………....xvii

Acknowledgements ……………………………………………………………………xxiv

Abstract ………………………………………………………………………….…....xxvii

Chapter 1: General Introduction

Phosphorus ………………………………………………………………………………..1

1.1.1 Phosphorus Compounds ………………………………………………………….2

1.1.2 The Phosphoryl …………………………………………………………………...4

1.2 Self-Doped Conjugated Polymers ………………………………………………...6

1.2.1 Conjugated Polymers …………………………………………………………..…6

1.2.2 Polyaniline ………………………………………………………………………..9

1.3 Phosphorus Based Flame Retardants ……………………………………………10

1.3.1 Combustion ……………………………………………………………………...10

1.3.2 Flame Retardants ………………………………………………………………..11

1.4 Lithium-ion Batteries ……………………………………………………………13

1.4.1 Batteries …………………………………………………………………………13

1.4.2 Lithium-ion Batteries ……………………………………………………………13

1.5 Works Cited …………………………………………………………….………16

Chapter 2: Synthesis and Characterization of Phosphorus Containing Polyaniline

2.1 Introduction ……………………………………………………………………..19

2.2 Results and Discussion ………………………………………………………….22

2.2.1 Functionalized Monomer ………………………………………………………..22

2.2.2 X-Ray Diffraction Study of 2.3 ………………………………………………....26

2.3 Electrochemical Synthesis and Characterization of Polymers …………………..28

2.4 Chemical Synthesis and Characterization of Polymers …………………………33

2.5 Chemical Synthesis of Copolymers 2.8-2.14 ……………………………………38

2.6 Conclusion ………………………………………………………………………40

2.7 Experimental …………………………………………………………………….42

2.8 Works Cited……………………………………………………………………..56

Chapter 3: Synthesis and Characterization of Bifunctional Electrolytes for Lithium-Ion

Batteries

3.1 Introduction ……………………………………………………………………..58

3.2 Results and Discussion ………………………………………………………….60

3.2.1 Synthesis of Lithium Cyclic Triol Borate Salts ………………………………...60

3.2.2 Efforts towards Phosphorus Containing Lithium Cyclic Triol Borate Salts ……63

3.2.3 Synthesis of H2-DPC ……………………………………………………………66

3.2.4 X-Ray Crystallographic Study of H2-DPC ……………………………………...67

3.2.5 Acidity of H2-DPC ………………………………………………………………68

3.2.6 Synthesis of DPC Based FRIONs …..…………………………………………...69

3.2.7 X-Ray Crystallographic Study of Li[B(DPC)(oxalato) …………………………71

3.2.8 TGA of DPC FRIONs …………………………………………………………...72

3.2.9 Microcombustion Calorimetry of DPC FRIONs ………………………………..73

3.2.10 DPN Synthesis …………………………………………………………………..75

3.2.11 Crystallographic Study of H2-DPN ……………………………………………..76

3.2.12 Synthesis of DPN FRIONs ……………………………………………………...78

3.2.13 TGA of Li[B(DPN)2] ……………………………………………………………79

3.2.14 Efforts Toward Other FRION systems ………………………………………….80

3.2.15 Synthesis of Ethyl-(2-hydroxyphenyl)phosphonic Acid Ester ………………….80

3.2.16 Efforts Toward Ethyl-(2-hydroxyphenyl)phosphonic Acid Ester Based FRION 82

3.2.17 Efforts Toward Biphenol FRIONs ……………………………………………...83

3.2.18 Efforts Towards Lithium Biphenolphosphonate Borate FRIONs ………………85

3.3 Conclusions ……………………………………………………………………..86

3.4 Experimental ……………………………………………………………………88

3.5 Works Cited ……………………………………………………………………134

Appendix A – Attempts to synthesize phosphorus containing CTB …………………..137

Appendix B – Efforts towards Novel 1,3-Benzoxaphospholes and Use as Ligands …..172

Appendix C – Crystal Structure Determination and Data ……………………………..180

Bibliography …………………………………………………………………………...273

List of Charts

Chart 1.1: Examples of conjugated polymers…………………………………………….7

Chart 2.1: Some functionalized polyanilines……………………………………………21

Chart 3.1: Promising LIB additives…………………………………………………….59

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List of Tables

Table 2.1: Yields of copolymers along with the minimum amount of copolymer prepared…………………………………………………………………………………38

Table 3.1: MCC results for FRIONs and LiBOB………………………………………73

Table C.1: Crystal data and structure refinement for H2-DPC……………….……….180

Table C.2: Atomic coordinates (x 104) and equivalent isotropic displacement parameters.

…………………………………………………………………………………………..181

Table C.3: Bond lengths [Å] and angles [°] for H2-DPC…………………………...…183

2 3 Table C.4: Anisotropic displacement parameters (Å x 10 ) for H2-DPC……………..185

Table C.5: Hydrogen coordinates (x 104) and isotropic displacement parameters (Å2 x

3 10 ) for H2-DPC………………………………………………………………………..187

Table C.6: Crystal data and structure refinement for Li[B(DPC)(Oxalato)]…………188

Table C.7: Atomic coordinates and equivalent isotropic displacement parameters for

Li[B(DPC)(Oxalato)]………………………………………………………………….190

Table C.8: Bond lengths [Å] and angles [°] for Li[B(DPC)(Oxalato)]……………….193

Table C.9: Anisotropic displacement parameters for Li[B(DPC)(Oxalato)]……..…..199

Table C.10: Hydrogen coordinates and isotropic displacement parameters for

Li[B(DPC)(Oxalato)]……………………………………………………………….…202

Table C.11: Crystal data and structure refinement for H2-DPN…………………..…..204

Table C.12: Atomic coordinates and equivalent isotropic displacement parameters for

H2-DPN……………………………………………………………………………...…207

Table C.13: Bond lengths [Å] and angles [°] for H2-DPN…………………………....209

Table C.14: Anisotropic displacement parameters for H2-DPN. …………………….211

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Table C.15: Hydrogen coordinates and isotropic displacement parameters for H2-DPN.

………………………………………………………………………..……….………..213

Table C.16: Crystal data and structure refinement for U……………..……………….214

Table C.17: Atomic coordinates and equivalent isotropic displacement parameters for U.

…………………………………………………………………………………………..216

Table C.18: Bond lengths [Å] and angles [°] for U……………………………………223

Table C.19: Anisotropic displacement parameters for U………………………………250

Table C.20: Hydrogen coordinates and isotropic displacement parameters for U…….257

Table C.21: Crystal data and structure refinement for B.2…………………………....262

Table C.22: Atomic coordinates and equivalent isotropic displacement parameters for

B.2. …………………………………………………………………………………….263

Table C.23: Bond lengths [Å] and angles [°] for B.2. ………………………….……..267

Table C.24: Anisotropic displacement parameters for B.2. …………………………..271

List of Figures

Figure 1.1: Structure of ATP. …………………………………………………………….1

Figure 1.2: Name and bonding examples of triphenylphosphine and triphenylphosphine oxide. ……………………………………………………………………………………...2

Figure 1.3: Phosphines as σ-donors and π-acceptors. ……………………………………3

Figure 1.4: Early depiction of the bond between phosphorus and oxygen. ……………...5

Figure 1.5: Resonance structures describing the phosphoryl bond. ……………………..5

Figure 1.6: Graphical representation of PO bonding as a σ-bond stabilized by 3 π back-

bonds. ………………………………………………………….………………………….6

Figure 1.7: Non-degenerate structures found in PPP. ……………………………………8

Figure 2.1: Protonic doping of emeraldine base. ……………………………………….20

Figure 2.2: Commonly accepted phospho-Fries rearrangement mechanism. ….……….23

Figure 2.3: Proposed phosphoramidate reaction……………….………………………..24

Figure 2.4: 31P NMR spectra of the phospho-Fries rearrangement product when

quenched by D2O (top) and 2.1 (bottom)…………….…………………………………. 24

Figure 2.5: ORTEP diagram of 2.3…….……………………………………………….27

Figure 2.6: ORTEP diagram of three units of 2.3 shows the intermolecular and

intramolecular hydrogen bonds (shown as dotted lines) of the compound in the solid

state. ……………………………………………………………………………………..28

Figure 2.7: Electropolymerization of a saturated solution of 2.3 in 1.0 M aqueous

hydrochloric acid on the glassy carbon working electrode with repeated cycling from -0.2

V to 0.95 V vs. SCE over 70 scans………………………………………………………29

Figure 2.8: Cyclic voltammograms of a film of 2.4 over ten cycles in 1.0 M aqueous

hydrochloric acid from -0.20 V to +0.95 V vs. SCE…………………………………….30

Figure 2.9: Degradation of polyaniline film over 10 cycles in 1.0 M aqueous

hydrochloric acid on the glassy carbon working electrode with repeated cycling from -

0.235 V to +0.95 V………………………………………………………………………31

Figure 2.10: Cyclic voltammograms of a saturated solution of 2.2 in 1.0 M aqueous

hydrochloric acid on the glassy carbon working electrode with repeated cycling from -0.2

V to 0.8 V vs. SCE over 70 scans………………………………………………………..32

Figure 2.11: UV-Vis Spectra of polymers 2.4, 2.5, 2.6 and 2.7; measured in 10-7 M

aqueous solutions………………………………………………………………………...35

Figure 2.12: Comparison of the FTIR spectra of the progressively deprotonated polymers

2.4-2.7, showing the 2000-500 cm-1 region……………………………………………...37

Figure 2.13: 31P{H} NMR Spectrum of 2.1…………………………………………….43

Figure 2.14: 31P NMR Spectrum of 2.1…………………………………………………44

Figure 2.15: 1H NMR Spectrum of 2.1………………………………………………….45

Figure 2.16: 31P{H} NMR Spectrum of 2.2…………………………………………….46

Figure 2.17: 1H NMR Spectrum of 2.2………………………………………………….47

31 Figure 2.18: P{H} NMR Spectrum of 2.3 in D2O…………………………………….48

Figure 2.19: 1H NMR Spectrum of 2.3………………………………………………….49

Figure 3.1: Prepared lithium CTB salts and their yields………………………………...62

Figure 3.2: TGA of LiCMeBPh and LiCEtBPh…………………………………………...63

Figure 3.3: Target lithium PCTB salts…………………………………………………64

Figure 3.4: Initial FRION………………………………………………………………..65

Figure 3.5: Molecular structure of H2-DPC in the solid state…………………………..67

Figure 3.6: Intra- and intermolecular hydrogen bonding between two molecules of H2-

DPC in the solid state……………………………………………………………………68

Figure 3.7: Molecular structure of Li[B(DPC)(oxalato)] in the solid state…………….72

Figure 3.8: TGA of lithium borate FRIONs…………………………………………….73

Figure 3.9: Molecular structure of H2-DPC. Hydrogen bonding shown in dotted lines.

Non-relevant hydrogen atoms omitted for clarity………………………………………..77

Figure 3.10: Packing diagram of H2-DPN in the solid state. Hydrogens omitted for

clarity…………………………………………………………………………………….78

Figure 3.11: TGA of Li[B(DPN)2]. …………………………………………………….80

Figure 3.12: Target FRIONs…………………………………………………………….81

Figure 3.13: 31P NMR spectrum of reaction products between 3.5, LiOtBu, and

B(OMe)3………………………………………………………………………………….83

Figure 3.14: Lithium bis[2,2'-biphenyldiolato(2-)-O,O']borate…………………………84

Figure 3.15: Target FRION salt lithium bis[2,2'-biphenyl(tetraethyl)phosphinato- diolato(2-)-O,O']borate………………………………………………………………….84

Figure 3.16: 31P NMR spectrum of the reaction product of 3.7, boric acid, and lithium t-

butoxide…………………………………………………………………………………..86

1 Figure 3.17: H NMR Spectrum of recrystallized, dried, LiCEtBPh in DMSO-d6………90

11 Figure 3.18: B NMR Spectrum of of recrystallized, dried, LiCEtBPh in DMSO-d6….. 91

13 Figure 3.19: C NMR Spectrum of of recrystallized, dried, LiCEtBPh in DMSO-d6…...92

1 Figure 3.20: H NMR Spectrum of LiCEtBPh intermediate……………………………..93

1 Figure 3.21: H NMR Spectrum of LiCEtBPh in DMSO-d6……………………………..94

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1 Figure 3.22: H NMR Spectrum of n-butylboronic acid in DMSO-d6………………….95

1 Figure 3.23: H NMR Spectrum of n-butyl cyclic intermediate in DMSO-d6…………..96

1 Figure 3.24: H NMR Spectrum of LiCEtBn-Bu in DMSO-d6………………………………………… 97

31 Figure 3.25: P{H} NMR Spectrum of 3.1 in CDCl3…………………………………..98

1 Figure 3.26: H NMR Spectrum of 3.1 in CDCl3……………………………………….99

31 Figure 3.27: P{H} NMR Spectrum of H2-DPC in CDCl3…………………………...100

1 Figure 3.28: H NMR Spectrum of H2-DPC in CDCl3………………………………..101

31 Figure 3.29: P{H} NMR Spectrum of Li[B(DPC)2] in DMSO-d6………………….104

1 Figure 3.30: H NMR Spectrum of Li[B(DPC)2] in DMSO-d6……………………….105

13 Figure 3.31: C{H} NMR Spectrum of Li[B(DPC)2] in DMSO-d6………………….106

11 Figure 3.32: B{H}NMR Spectrum of Li[B(DPC)2] in DMSO-d6…………………..107

31 Figure 3.33: P{H} NMR Spectrum of Li[B(DPC)(oxalato)] in DMSO-d6…………108

1 Figure 3.34: H NMR Spectrum of Li[B(DPC)(oxalato)] in DMSO-d6……………...109

13 Figure 3.35: C{H} NMR Spectrum of Li[B(DPC)(oxalato)] in DMSO-d6…………110

11 Figure 3.36: B{H}NMR Spectrum of Li[B(DPC)(oxalato)] in DMSO-d6………….111

31 Figure 3.37: P{H} NMR Spectrum of Li[B(DPC)F2] in DMSO-d6………………...112

1 Figure 3.38: H NMR Spectrum of Li[B(DPC)F2] in DMSO-d6……………………...113

13 Figure 3.39: C{H} NMR Spectrum of Li[B(DPC)F2] in DMSO-d6……………….114

11 Figure 3.40: B{H}NMR Spectrum of Li[B(DPC)F2] in DMSO-d6…………………115

19 Figure 3.41: F NMR Spectrum of Li[B(DPC)F2] in DMSO-d6…………………….116

31 Figure 3.42: P{H} NMR spectrum of 3.2 in CDCl3…………………………………117

1 Figure 3.43: H NMR spectrum of 3.2 in CDCl3………………………………………118

31 Figure 3.44: P{H} NMR spectrum of H2-DPN in CDCl3……………………………119

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1 Figure 3.45: H NMR spectrum of H2-DPN in CDCl3………………………………...120

31 Figure 3.46: P{H} NMR of Li[(DPN)2B] in DMSO-d6……………………………..121

1 Figure 3.47: H NMR of Li[(DPN)2B] in DMSO-d6………………………………….122

13 Figure 3.48: C{H} NMR Spectrum for Li[(DPN)2B]. …………………………….. 123

31 Figure 3.49: P{H} NMR Spectrum of 3.6 in CDCl3. ……………………………….124

1 Figure 3.50: H NMR Spectrum of 3.6 in CDCl3. …………………………………….125

31 Figure 3.51: P{H} NMR Spectrum of 3.7 in CDCl3. ……………………………….126

1 Figure 3.52: H NMR Spectrum of 3.7 in CDCl3. …………………………………….127

31 Figure 3.53: P{H} NMR of 3.5 in CDCl3. ………………………………………….128

1 Figure 3.54: H NMR of 3.5 in CDCl3………………………………………………...129

Figure 3.55: 31P{H} NMR Spectrum of U…………………………………………….130

Figure 3.56: 1H NMR Spectrum of U. …………………………….…………….…….131

Figure 3.57: Full Molecular structure of a network of a crystal isolated from U. …….131

Figure A-1: 31P{H} NMR Spectrum of 4-88. ……………….…………….…………..137

Figure A-2: 31P{H} NMR Spectrum of 4-90. ……………….…………….…………..138

Figure A-3: 31P{H} NMR Spectrum of 4-91. ……………….…………….…………..140

Figure A-4: 31P{H} NMR Spectrum of 4-88. ……………….…………….…………..140

Figure A-5: 31P{H} NMR Spectrum of 4-93. ……………….…………….…………..142

Figure A-6: 31P{H} NMR Spectrum of 4-95. ……………….…………….…………..143

Figure A-7: 1H NMR Spectrum of 4-95. ……………….…………….……………….144

Figure A-8: 31P{H} NMR Spectrum of 4-96. ……………….…………….…………..145

Figure A-9: 1H NMR Spectrum of 4-96……………….…………….………………...146

Figure A-10: 31P{H} NMR Spectrum of 4-97……………….…………….…………..147

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Figure A-11: 1H NMR Spectrum of 4-97. ……………….…………….……………...148

Figure A-12: 31P{H} NMR Spectrum of 4-98. ……………….…………….…………149

Figure A-13: 31P{H} NMR Spectrum of 4-99. ……………….…………….…………150

Figure A-13: 1H NMR Spectrum of 4-99……………….…………….……………….151

Figure A-14: 31P{H} NMR Spectrum of 5-03. ……………….…………….…………152

Figure A-15: 1H NMR Spectrum of 5-03. ……………….…………….……………...153

Figure A-16: 31P{H} NMR Spectrum of 5-06. ……………….…………….…………154

Figure A-17: 31P{H} NMR Spectrum of 5-10. ……………….…………….…………155

Figure A-18: 31P{H} NMR Spectrum of 5-11. ……………….…………….…………156

Figure A-19: 31P{H} NMR Spectrum of aliquot 1 of 5-13. ……………….………….158

Figure A-20: 31P{H} NMR Spectrum of final product of 5-13. ………….…………...159

Figure A-21: 1H NMR Spectrum of final product 5-13. ………….…………………...160

Figure A-22: 31P{H} NMR Spectrum of 5-14………….…………………...... 161

Figure A-23: 31P{H} NMR Spectrum of 5-15………….…………………...... 163

Figure A-24: 31P{H} NMR Spectrum of 5-16. ………….…………………...... 165

Figure A-25: 31P{H} NMR Spectrum of 5-17………….…………………...... 166

Figure A-26: 31P{H} NMR Spectrum of 5-18………….…………………...... 167

Figure A-27: 31P{H} NMR Spectrum of 5-19………….…………………...... 168

Figure A-28: 1H NMR Spectrum of 5-19………….…………………...... 169

Figure A-29: 31P{H} NMR Spectrum of 5-25………….…………………...... 170

Figure A-30: 1H NMR Spectrum of 5-25………….…………………...... 171

Figure B.1: 31P{H} NMR spectrum of B.1………….…………………...... 173

Figure B.2: 1H NMR spectrum of B.1………….…………………...... 174

Figure B.3: Aromatic Region of 1H NMR spectrum of B.1………….………………..175

Figure B.4: 13C{H} NMR Spectrum of B.1………….…………………...... 176

Figure B.5: 31P{H} NMR Spectrum of reaction 1-89. ………….…………………...... 177

Figure B.6: Molecular structure of B.2. ………….…………………...... 179

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List of Schemes

Scheme 1.1: Conversion between the three oxidation states of polyaniline. …………….9

Scheme 1.2: Flame propagation reactions. ………….…………………...... 11

Scheme 1.3: Phosphorus flame retardant radical scavenger reactions…………………..12

Scheme 2.1: Literature preparation of 2.3………….…………………...... 22

Scheme 2.2: Original plan for the preparation of 2.3………….………………………...22

Scheme 2.3: Optimized synthesis of 2.3………….…………………...... 25

Scheme 2.4: Chemical synthesis of 2.4. ………….…………………...... 33

Scheme 2.5: Synthesis of 5, 6, and 7. ………….…………………...... 34

Scheme 2.6: Synthesis of copolymers………….…………………...... 38

Scheme 3.1: Literature preparation of CTB Salts. ………….…………………...... 60

Scheme 3.2: Improved synthesis of LiCEtBPh. ………….…………………...... 61

Scheme 3.3: Proposed synthetic route to phosphorus containing CTBs………………...64

Scheme 3.4: Preparation of H2-DPC………….…………………...... 67

Scheme 3.5: Synthesis of lithium DPC borate salts. ………….…………………...... 71

Scheme 3.6: Preparation of H2-DPN. ………….…………………...... 76

Scheme 3.7: Synthesis of DPN based FRIONs. ………….…………………...... 79

Scheme 3.8: Syntheis of 3.5. ………….…………………...... 82

Scheme 3.9: Synthesis of 2,2'-biphenyl(tetraethyl)diphosphinato-diol………………….85

Scheme 3.10: Reaction of 3.7 with B(OH)3 and LiOtBu………………………………..85

Scheme A.1: Reaction 4-88. ………….…………………...... 137

Scheme A.2: Reaction 4-90. ………….…………………...... 138

Scheme A.3: Reaction 4-91………….…………………...... 139

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Scheme A.4: Reaction 4-88. …….…………………...... 140

Scheme A.5: Reaction 4-93. …….…………………...... 141

Scheme A.6: Reaction 4-95. …….…………………...... 142

Scheme A.7: Reaction 4-96. …….…………………...... 144

Scheme A.8: Reaction 4-97. …….…………………...... 146

Scheme A.9: Reaction 4-98. …….…………………...... 148

Scheme A.10: Reaction 4-99. …….…………………...... 149

Scheme A.11: Reaction 5-03. …….…………………...... 151

Scheme A.12: Reaction 5-06. …….…………………...... 153

Scheme A.13: Reaction 5-10. …….…………………...... 155

Scheme A.14: Reaction 5-11. …….…………………...... 156

Scheme A.15: Reaction 5-13. …….…………………...... 157

Scheme A.16: Reaction 5-14. …….…………………...... 160

Scheme A.17: Reaction 5-15. …….…………………...... 162

Scheme A.18: Reaction 5-16 through 5-19. …….…………………...... 163

Scheme A.19: Reaction 5-25. ………………………………………………………….169

Scheme B.1: Synthesis of B.1. …….…………………...... 172

Scheme B.2: Reaction 1-89. …….…………………...... 176

Scheme B.3: Synthesis of B.2. …….…………………...... 178

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List of Abbreviations and Symbols

% Percent

° Degree

δ Delta

γ Gamma

λ Lambda

π Pi

• Radical

σ Sigma

Å Angstrom

Anal. Analytical

ATP Adenosine triphosphate

aq Aqueous

11B NMR Boron-11 nuclear magnetic resonance

B(OH)3 Boric acid

C Celsius

CaH2 Calcium hydride

Calc’d Calculated

CDCl3 Deuterated chloroform

CH2Cl2 Dichloromethane cm-1 Reciprocal centimeters

C=O Carbonyl

CTB Cyclic triol borate

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13C{1H} NMR Proton decoupled carbon-13 nuclear magnetic resonance spectroscopy

d Doublet

D2O Deuterium oxide

dd Doublet of doublets

DMF Dimethylformamide

DMSO Dimethyl sulfoxide

DMSO-d6 Deuterated dimethyl sulfoxide

DPC Diphosphinato catechol

DPN Diphosphinato napthalene

Eq. Equivalent

ESI Electrospray ionization

Et2O Diethyl ether

EtOH Ethanol

19F NMR Fluorine-19 nuclear magnetic resonance

FET Field effect transistor

FRION Flame retardant ion

FT-IR Fourier transform infrared

g Gram

GPC Gel permeation chromatography

H Proton

h Hour

1H NMR Proton nuclear magnetic resonance

H2O2 Hydrogen peroxide

H2SO4 Sulfuric acid

HCl Hydrochloric acid

HRMS High-resolution mass spectrometry

HRR Heat release rate

Hz Hertz

IR Infrared

J J-coupling in NMR

kJ Kilojoules

kcal Kilocalories

kHz Kilohertz

L Liter

LiBOB Lithium Bis(oxalato)borate

LIB Lithium-ion battery

LiCl Lithium chloride

LDA Lithium diisopropylamide

LiOH Lithium hydroxide

LiOtBu Lithium tButoxide

LiPF6 Lithium hexafluorophosphate

m Meta

m Meter or multiplet

m/z Mass-to-charge ratio

M Molar

M-1 Reciprocal molar

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MCC Microcombustion Calorimetry

MeCN Acetonitrile

MeOH Methanol

MgSO4 Magnesium sulfate

MHz Megahertz

min Minute

mL Milliliter

mM Millimolar

mm Millimeter

mmol Millimole

mol Mole

Mol Wt Molecular weight

mp Melting point

N2 Nitrogen gas

NLO Nonlinear optical

NaCl Sodium chloride

NaH Sodium hydride

NaHCO3 Sodium bicarbonate

Na2SO4 Sodium sulfate

Na2(SO4)2 Sodium persulfate

NMP N-Methyl-2-pyrrolidone

NMR Nuclear magnetic resonance

o Ortho

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OLED Organic light emitting diode

OMe Methoxy p Para pKa - Log of the acid dissociation constant

31P{1H}NMR Proton decoupled phosphorus-31 nuclear magnetic resonance

31P NMR Phosphorus-31 nuclear magnetic resonance

PA Polyacetylene

P=O Phosphoryl

PANI Polyaniline

ppm Parts per million

PPP Polyparaphenylene

PPV Polyparaphenylene vinylene

PPy Polypyrrole

PT Polythiophene q Quartet

R Alkyl side chain attached to a core molecule

RT Room temperature s Singlet

SCE Saturated calomel electrode

SEI Solid electrolyte interface

SOCl2 Thionyl chloride t Triplet tBuOH tButyl alcohol

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TGA Thermal gravimetric analysis

THF Tetrahydrofuran

THPC Tetrakis(hydroxymethyl)phosphonium chloride

THMPO Tris(hydroxymethyl)phosphine oxide

TMS Trimethylsilyl

TMS Tetramethylsilyl (NMR Spectroscopy)

UV Ultraviolet

UV-vis Ultraviolet-visible spectroscopy

V Volts

W Watt

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Acknowledgements

I could not have completed this project alone. I have benefitted from the kindness of others at every step along the way, and the list of people to thank is long. I am forever grateful to those who reached back when I reached out for help.

Thank you to my advisor, Dr. John Protasiewicz for his guidance and patience. It has truly been an honor working in your lab. You are an excellent advisor and scientist, but you are an even better person. You transformed an uncertain student into the scientist

I am today. Words cannot express how much I respect and thank you.

Thank you to my committee members, Dr. Thomas Gray, Dr. Malcolm Kenney,

Dr. Daniel Scherson, and Dr. Stuart Rowan. Thank you for your time and assistance in reviewing my work and thesis.

Thank you to Case Western Reserve University, the United States Department of

Energy, and the National Science Foundation for financial support. Thank you to the scientists who assisted with this work including Dr. Alexander Morgan of the University of Dayton, for performing microcombustion calorimetry experiments; Dr. Arnold

Rheingold of the University of California, San Diego, for performing X-ray crystallography; Dr. Nihal Deligonul for assistance with X-ray crystallography; Dr. Dale

Ray for assistance with NMR spectroscopy; Dr. Michelle Rasmussen for helping me to learn electrochemistry and showing me how to perform cyclic voltammetry; and Dr.

Richard West for lending me electrodes, and not being mad when I forgot to return them.

Thank you to Dr. Scherson. It has been a pleasure collaborating with you on my projects. Thank you for the advice on electrochemistry and helping to make great slides, reports, and presentations.

xxv

To my professors at Case Western Reserve University, Dr. Zagorski, Dr. Lee, Dr.

Dunbar, Dr. Gray, Dr. Viswanathan, and Dr. Protasiewicz, thank you teaching me the

highest level of our craft. To my professors from Mercyhurst University, Dr. Barranger-

Mathys, Dr. Williams, and especially Dr. Brown and Dr. Chambers, thank you for helping me navigate chemistry. To my all of my other teachers, especially Mr. Bowen,

Mrs. Santos, Ms. Squiggle, Mr. Mitchell, and Ms. Noble, thank you.

Thank you to Dr. Thomas Gray, Director of The Institute for World Domination

Through the Study of Metal-Carbon Bond Formation and Metal-Nitrogen Bond

Formation, and the Gray group for letting me borrow chemicals and glassware, sharing your knowledge, and letting me bounce ideas off you. If only gold and phosphorus had a diagonal relationship.

Thank you to past and present Protasiewicz group members for your support, advice, and friendship. Thank you to Dr. Marlena Washington, who trained me, took me under her wing, and showed me how to work in lab. Thank you to Dr. Andrew

Shaffer, who helped me to perfect my technique and hone my craft. Thank you to Dr.

Babu Gudimetla, Dr. Feng “Phoenix” Laughlin, Shanshan Wu, Alex Beckman, and Josh

Gaffen. It has been such a pleasure learning chemistry with you. I’m proud to be a member of the Protasiewicz group.

Thank you to my friends who helped me through the hard times and celebrated with me in the good times. Thank you especially to Dan Benoit and Mark

Stampfle for making me feel cool being the big weirdo that I am.

Thank you, Amberle Browne. Your kind heart has kept me from going crazy at times and brought me back when I was slightly less-than-sane.

xxvi

Thank you, Dr. Alden Voelker. Being friends with you was the best side product of being in graduate school. You have been the best friend a person could ask for, and I couldn’t have gotten through this without you. I will always treasure our friendship.

Thank you, Tom, Mary, and Alex Yablonsky for being so supportive and helpful.

You have always been cheering for me, and I am fortunate to have you in my life.

Thank you, Dave, Tom, and Mary K. Rectenwald. You all are truly amazing. I can’t think of you all and not smile. I have taken so many 5 minute vacations laughing at your pictures, thinking of our good times, and texting and talking to you. Thank you from the bottom of my heart for your love and support.

To my grandparents, thank you. I love you and I miss you.

Thank you Mom and Dad, Sherry and Frank Rectenwald for reading to me, taking me to the science center, always encouraging me, and always supporting me. I am the person I am today because of your care and love.

To my wife, Elise. Thank you for your infinite support through this process. You inspire

me, challenge me, and make me a better person every single day. Thank you for motivating me when I wanted to sit in my chair. I have no idea where I would be without

you, but I know I can go anywhere and do anything as long as I’m with you.

xxvii

Phosphorus-Containing Conjugated Polymers and Bifunctional Electrolytes

Abstract

MICHAEL F. RECTENWALD

Several novel phosphorus-containing polyanilines and lithium salts were

designed, synthesized, and characterized. The self-doping polymer poly(2-

aminophenylphosphonic acid) has been prepared by electrochemical and chemical

oxidative polymerization of 2-aminophenylphosphonic acid. The solid state structure of

2-aminophenylphosphonic acid has been determined by an X-ray diffraction study. Films

of poly(2-aminophenylphosphonic acid) prepared by electrochemical polymerization have been analyzed using cyclic voltammetry. The phosphonic acid group attached to the polymer increases the stability of poly(2-aminophenylphosphonic acid) to oxidations more positive than 0.8 V SCE. Chemically synthesized poly(2-aminophenylphosphonic acid) has been characterized by UV-vis and FTIR spectroscopy. Sodium salts of poly(2- aminophenylphosphonic acid) were synthesized by progressive neutralization of phosphonic acid groups using sodium hydroxide, yielding water soluble polymers with varying degrees of protonation. Copolymers of 2-aminophenylphosphonic acid and aniline have been synthesized where the ratios of 2-aminophenylphosphonic acid to aniline were varied.

xxviii

The functionalized catecholate, tetraethyl (2,3-dihydroxy-1,4-

phenylene)bis(phosphonate), has been used to prepare a series of lithium salts

Li[B(DPC)(oxalato)], Li[B(DPC)2], and Li[B(DPC)F2]. These anions were designed to

impart flame-retardant properties for their use as potential flame-retardant ions

(FRIONs), additives, or replacements for other lithium salts for safer lithium-ion batteries. The new materials were fully characterized, and the single-crystal structure of

Li[B(DPC)(oxalato)] has been determined. Thermogravimetric analysis of the three lithium salts show that they are thermally stable up to around 200 °C. Pyrolysis combustion flow calorimetry reveals that these salts produce high char yields upon combustion.

The functionalized dihydroxynaphthalene (2,3-Dihydroxy-1,4- diphosphinatonaphthalene) has been prepared in a similar manner to tetraethyl (2,3- dihydroxy-1,4-phenylene)bis(phosphonate). This compound has been structurally characterized and used to create a lithium salt Li[B(DPN)2] which is stable up to 230 °C.

Several other FRION precursors have been prepared and characterized.

xxix

Chapter 1: General Introduction

1.1 Phosphorus

Elemental phosphorus was first observed in 1669 by the alchemist Hennig Brandt

in an attempt to isolate gold from human urine.1 He observed the luminescence that gives

phosphorus its name, “phōs-phoros,” Greek for light-bringer. It was first recognized as

an element by Lavosier in 1777, and is the first element isolated that is found in nature

3- 1 only as a derivative form (usually the anion center in a phosphate salt, PO4 ). Today,

phosphorus-containing compounds are ubiquitous and significant in chemistry.

Phosphorus compounds play an important role in biological systems. Essentially

every thermodynamically unfavorable metabolic process is driven by the

thermodynamically favorable displacement of a phosphorus monoester or anhydride.2

Most living organisms use adenosine triphosphate (ATP), seen in Figure 1.1, as an

“energy currency” for short term energy use and transfer.2,3 Phospholipids like

phosphatidylcholines make up the lipid bilayer, the cell membrane used in almost all living organisms and many viruses.4 Phospholipids are also used in the membranes

surrounding the cell nucleus and other cellular structures.

O O O

P P P O N HO O O O N OH OH OH NH2

HO N OH N

Figure 1.1: Structure of ATP.

Synthetic organophosphorus chemistry enjoys a robust history and exciting future.

Phosphorus shares a diagonal relationship with carbon due to its similar electronegativity.

The introduction of phosphorus atoms into carbon-based systems is a common thread in modern phosphorus research due to this relationship. Low coordinate phosphorus has been called “The Carbon Copy” due to similarities in behavior and structure. Research with phosphorus blurs the traditional borders between organic, inorganic, biological, and materials chemistry.5

1.1.1 Phosphorus Compounds

Phosphorus compounds have many structural possibilities. The phosphorus atom may directly bond with one to six other atoms and may form multiple bonds with several elements.3 In order to organize these compounds, phosphorus is assigned a coordination number that states the number of directly attached atoms. This number is designated by

σ. The valency, or total number of bonds attached to phosphorus, is described by λ. An example of the naming conventions and organizational scheme of phosphorus compounds can be seen in Figure 1.2. For example, the phosphorus on triphenylphosphene (PPh3) which is attached to three carbon atoms and contains three bonds is described as σ3λ3.

Triphenylphosphine oxide (O=P(Ph)3), which is attached to four atoms centers but contains five formal bonds may be described as σ4λ5.3

P P Ph Ph Ph Ph Ph Ph

Triphenylphosphine Triphenylphosphine Oxide σ3λ3 σ4λ5

Figure 1.2: Name and bonding examples of triphenylphosphine and triphenylphosphine

oxide.

A λ3 phosphorus species with a lone pair of electrons may be readily oxidized to a λ5

species. Conversion from a λ5 compound to a λ3 compound is much more difficult.

Phosphorus reagents are commonly used in coordination chemistry and catalysis.

Like nitrogen, the lone pair on phosphorus can be donated to a metal. Unlike nitrogen,

phosphines are π-electron acceptors.6,7 The σ* orbitals of the P-R bond are capable of accepting electrons from the metal. A schematic representation of the bonding scheme is shown in Figure 1.3. A phosphine’s ability to act as an electron acceptor is determined primarily by the electronegativity of the R group attached to it. More electronegative substituents reduce the energy of the σ* orbital, and allow for a more effective donation

7 of π electrons from the metal center to the phosphorus atom. PF3 will accept π electrons

as readily as carbon monoxide, whereas compounds containing P-C bonds are significantly less accessible for π donation. This ability to tune the ligand on a metal is highly desirable.

R R M P M P R R R R

σ∗ M(dσ) P(n) M(dπ) PR( )

Figure 1.3: Phosphines as σ-donors and π-acceptors.

1.1.2 The Phosphoryl

The phosphoryl group is extraordinarily important in organophosphorus chemistry. In the presence of oxygen, a λ3 phosphorus atom will develop a phosphorus oxygen double bond, as these compounds are thermodynamically favorable. The oxophilic nature of phosphorus is used to drive several reactions involving organophosphorus, as this bond has a large bond dissociation energy (128-139 kcal/mol).8 Current convention represents the phosphoryl as P=O, however this bond is

not similar to C=O in any way. Calling the bond between phosphorus and oxygen a

double bond is not wholly accurate, as the conventional method of drawing a double

bond does not accurately reflect the polarization between the two atom centers.9 Also,

this double bond seemingly violates the octet rule. Experimental and computational

studies show the phosphoryl bond is strong, polar, and short.10 Early literature often

represented the structure of compounds possessing a phosphoryl in a manner depicting an

octet of electrons on phosphorus, with a coordinate covalent bond going from phosphorus

to oxygen, as seen in Figure 1.4.3,9,10 This model has been rejected, however, as it does

not reflect the accurate bond strength, reactivity, or correct polarization of the

phosphoryl.

R P O 3

Figure 1.4: Early depiction of the bond between phosphorus and oxygen.

More recent representations describe the bond in a manner as shown in Figure

1.5; a mixture of resonance structures between a phosphorus-oxygen double bond seen in structure 1.1, and a charge separated species seen in structure 1.2. This representation better displays the polarization and location of electrons found in the phosphoryl, however the structure of 1.1 implies a true pπ-pπ bond, and the structure of 1.2 implies a

high reactivity towards nucleophiles at the phosphorus and electrophiles at the oxygen.

Neither of these representations is accurate.

R R

P O P O R R R R 1.1 1.2

Figure 1.5: Resonance structures describing the phosphoryl bond.

Chestnut and Savin11 provide an excellent model of bonding of phosphorus and

oxygen in their work from 1999. By modeling H3P=O using the electron localization

function (ELF) method, they provide evidence for a polarized σ bond between

phosphorus and oxygen combined with a staggered trigonal arrangement of electron lone

pairs on oxygen. The lone pairs on oxygen are stabilized by π back-bonding from the

oxygen onto the degenerate antibonding orbitals of the σ bonds between phosphorus and

hydrogen. This transfer of electron density from a π orbital to a σ* orbital is well known

in organic chemistry as negative hyperconjugation.12 A graphical representation of this

donor-acceptor relationship can be seen in Figure 1.6.

P O

Figure 1.6: Graphical representation of PO bonding as a σ-bond stabilized by 3 π back-

bonds (arrows).

For convenience and to comply with current convention, the phosphoryl will be

referred to and drawn as P=O. This representation is done with the understanding that the

phosphoryl does not engage in a pπ-pπ bond but is involved a more complicated and

interesting bonding motif. Regardless of the true nature of the P=O bond, it is certain

that the phosphoryl is short, strong, and highly polar.

1.2 Self-Doped Conjugated Polymers

1.2.1 Conjugated Polymers

Since the discovery in 1977 that doped polyacetylene conducts electricity,13

organic polymers with π-conjugation have emerged as some of the most important materials of the 20th century. The pioneering work done for the development of conductive polymers by Heeger, MacDiarmid, and Shirakawa earned the 2000 Nobel

Prize in Chemistry. Conjugated organic materials are already being used in commercial organic light-emitting diodes (OLEDs) in smart phones sold by LG, Nokia, and Samsung

and televisions sold by Samsung and LG. Conjugated polymers hold great potential for

use in electronic devices such as organic photovoltaic cells, field-effect transistors (FET),

electro-chromic or smart windows, nonlinear optical (NLO) devices, and polymeric sensors.14 Chart 1.1 shows the most commonly used building blocks of conjugated

polymers. Many conjugated materials feature heteroatoms in their backbone, most

notably polyaniline (PANI), polythiophene (PT), and polypyrrole (PPy). Phosphorus has been incorporated into π-conjugated polymers using building blocks such as poly(p- phenylenephosphaalkene),15 poly(phospholes),16 and poly(p-phenylene

phosphine).14,17,18

n n n n

Polyacetylene Polyparaphenylene Polyparaphenylene (PA) (PPP) vinylene (PPV)

H N S N n n H n n Polythiophene Polypyrrole Polyaniline (PT) (PPy) (PANI)

R P P P n n n n R Poly(paraphenylene Poly(phosphole) Poly(paraphenylene phosphaalkene) phosphine)

Chart 1.1 Examples of conjugated polymers.

The π-conjugated systems that contain aromatic rings have non-degenerate ground states.19,20 These states, shown for PPP in Figure 1.7, include a benzoid and

quinoid state. The benzoid state is slightly lower in energy than the quinoid state.19

When conjugated polymers are oxidized through the removal of one π electron, a radical

cation will form. The radical cation is delocalized throughout the polymer chain through

conjugation. In the solid state this is called a polaron.20 The polaron is what allows for

charge storage and transfer, and the polaron’s presence induces a quinoid bond sequence

along the π-conjugated polymer backbone.

n n Benzoid Quinoid

Figure 1.7: Non-degenerate structures found in PPP.

Increasing the conductivity of a polymer by oxidation is known as “p-doping.”

“N-doping” through the addition of electrons as a charge carrier is done as well, but is not

as commonly exploited as p-doping. P-doping can be accomplished by chemical,

electrochemical, or photochemical means.20 Typically, chemically doping a conducting

polymer involves the introduction of a large amount of dopant (up to 30% wt).20 The

large quantity of dopant necessary, its significant physical size, and extensive charge

transfer significantly alters the structure of the polymer. This distortion causes both the

polymer and dopant to act as ions leading to changes in polymer chain geometry.

1.2.2 Polyaniline

Polyaniline represents a unique type of conjugated polymer. It has a nitrogen heteroatom bridging two phenyl rings, yet the lone pair on nitrogen participates in conjugation. Although polyaniline has been known since 1862, its potential as a conducting polymer was not fully understood until it was investigated by Alan

Macdiarmid in 1986.21 Polyaniline can exist in three distinct oxidation states, as seen in

Scheme 1.1. The fully reduced form is leucoemeraldine base (all amine nitrogens), the fully oxidized form is pernigraniline (all imine nitrogens), and the half oxidized, half reduced form is emeraldine base (1:1 ratio of amine to imine nitrogens).14

H H N N

N N n H H Leucoemeraldine base

+ 2 e- - 2 e- + 2 H+ - 2 H+

H N N

N N n H Emeraldine base

+ 2 e- - 2 e- + 2 H+ - 2 H+

N N

N N n Pernigraniline

Scheme 1.1: Conversion between the three oxidation states of polyaniline.

Only the doped emeraldine base form of polyaniline is capable of conducting current, therefore reversible insulator to conductor behavior is observed. Polyaniline also shows yellow, green, blue, and violet electrochromic behavior. Oxidation state transitions of polyaniline are reversible and doping activity is variable based on pH,

making polyaniline one of the most tunable conjugated polymers. Polyaniline has

potential for use in rechargeable batteries, OLEDs, FETs, sensors, electrochromic

displays, and as an additive for corrosion resistance. Practical application of polyaniline

has been hindered by a high melting point, which makes it difficult to fuse into systems,

and low solubility in common organic solvents. Chapter 2 will detail attempts to

synthesize and characterize self-doping and water soluble phosphorus polyaniline polymers.

1.3 Phosphorus Based Flame Retardants

1.3.1 Combustion

Combustion of flammable materials is a complicated process involving several

coinciding combinations of heat and mass transfer, ﬂuid dynamics, and degradation

chemistry.22-25 Four major steps are involved in combustion: ignition, pyrolysis,

combustion, and feedback. At sufficiently high temperatures, the bonds between atoms

break causing the material to decompose or “pyrolyze” and evolve ﬂammable volatiles.

When C, H, and O bonds break, H•, OH•, CO, and other radical peroxides are evolved.

The combination of these products propagates combustion by the branching reaction seen

in Scheme 1.2.23,25

+ + H O2 OH O (1)

O + H2 OH + H (2) OH + CO H + CO 2 (3)

Scheme 1.2: Flame propagation reactions.

This process, called ignition, is exothermic and serves to overcome the energy

requirements needed for pyrolysis to occur.26 The combustion process of any organic

material can be thought of as a cascade of radical reactions initiated by heat. The gas

phase combustion process is commonly referred to as flame.26

1.3.2 Flame Retardants

The goal of flame retardants is to make materials less likely to ignite or make their ignition less efficient, not necessarily to make materials noncombustible.26 There are

four ways that flame retardants prevent the spread of flame: the pyrolysis process may be

modified to create a char layer rather than flammable volatiles; the flame may be cut off

from its oxygen supply; radical scavengers may be used to prevent the flame from

igniting; and releasing products to act as heat sink such as water or a char layer may

prevent the flow of heat to stop pyrolysis.26

Conventional flame retardants are active in either the vapor or condensed phase,

and employ physical and chemical mechanisms to prevent the spread of combustion.22-

25,27 One class of flame retardants are halogenated compounds which act as radical

scavengers in the vapor phase.28,29 However, halogen combustion products raise serious safety concerns because they produce dense, toxic smoke.29 Phosphorus-containing

materials have similar flame retardant properties as halogenated compounds without the

formation of toxic products.28-30 Phosphorus-containing flame retardants are broken

down into four categories: elemental red phosphorus, inorganic phosphates, organophosphorus compounds and chlororganophosphates.31 Phosphorus containing flame retardants can inhibit combustion via a radical scavenger mechanism, similar to halogenated flame retardants. Unlike halogenated compounds, the decomposition products of phosphorus flame retardants are relatively benign. Under high temperatures,

31 organophosphorus compounds form radicals such as HPO2∙, PO∙, PO2∙, and HPO∙.

These radicals can react with the highly reactive species H∙ and OH∙ in reactions 4 and 5 of Scheme 1.3 to produce more benign products than halogen combustion products.11

Final products include a charred layer of dehydrated polymeric phosphoric acid and

32 water, and are therefore much less likely to cause safety concerns. The H2O formed acts as a heat sink to dissipate the heat formed during combustion and the solid layer of char creates a barrier between virgin organic material and the heat, flame, and oxygen where combustion occurs.32 Char yield is one quantitative way of measuring the effectiveness of a phosphorus based flame retardant.

HPO2 + H PO + H2O (4) + + HPO2 OH PO2 H2O (5)

Scheme 1.3: Phosphorus flame retardant radical scavenger reactions.

The use of phosphorus based flame retardants incorporated into lithium-ion batteries will be discussed at length in chapter 3.

1.4 Lithium-ion Batteries

1.4.1 Batteries

A battery is one or more electrochemical cells which supply electricity. Batteries

utilize the conversion of chemical energy into electrical energy through redox reactions

that occur at the anode and cathode of the battery.33 Disposable batteries or primary

batteries are a cell or group of cells used for the generation of electrical energy intended

to be used until exhausted, and then discarded. Rechargeable batteries or secondary

batteries are a cell or group of cells used for the generation of electrical energy in which

the cell, after being discharged, may be restored to its original charged condition by an

electric current flowing in the opposite direction of the discharge current.33 The basic

battery components include an anode, cathode, and electrolyte. The anode should be

composed of a material capable of donating electrons, such as a metal or strong reducing

agent. The cathode should be an excellent electron acceptor. The electrolyte is the

physical separator of the anode and cathode and should be a pure ionic conductor.

1.4.2 Lithium-ion Batteries

Lithium-ion batteries are secondary batteries capable of high voltage (> 4V) and high energy density (~265-750 (Wh)L-1).34 Their ability to be recharged at any point in

the discharge cycle without a loss of capacity (memory effect) has made them desirable

over other secondary batteries such as nickel cadmium and nickel metal hydride. Though

lithium-ion batteries are ubiquitous in small electronics applications, their universal incorporation into large scale transport applications has significant hurdles. These

hurdles are based primarily on a design that values the highest possible energy density,

yet requires flammable components and solvents.35 There are many different materials

that can make up a lithium-ion battery. Generally, the anode of the battery is comprised

of carbon (graphite), the anode is a lithium cobalt oxide or lithium iron phosphate

material, and the electrolyte is a salt dissolved in a mixture of alkyl carbonates.36

Lithium-ion batteries typically employ a nonaqueous, organic solvent electrolyte

system. These nonaqueous systems present a challenge, as organic solvents have a lower

solvating ability of lithium salts than aqueous solutions. Lower solvating ability favors

ion pair formation over complete dissociation, which lowers the overall conductivity of

the electrolyte. Solvent systems typically consist of alkyl carbonates, such as ethylene

carbonate, dimethyl carbonate, and diethyl carbonate.37-39 These solvents are necessary

due to their ability to form a passivation film on the carbonaceous anode known as the

solid electrolyte interface (SEI).37,40 While not completely understood, the SEI film is

believed to be composed of the reduction products of the electrolyte and solvent, and is

necessary for intercalation of the lithium ion into the carbonaceous anode.38,40 Formation

of the film occurs upon the first charge of the battery, but will not occur afterwards.40

Any novel electrolyte with potential for use in a lithium-ion battery must form a SEI

upon first use, or the battery will not function.

Thermal runaway is an event that occurs when the battery electrode’s reaction

with the electrolyte becomes self-sustaining and the reactions enter an autocatalytic mode. These events can be catastrophic, and as the size of the battery increases, the potential for danger increases as well. Phosphorus flame retardants have been introduced into lithium-ion batteries; however there has been a decrease in battery capacity associated with their use. The goal of the work in Chapter 3 is to incorporate phosphorus containing flame retardant moieties onto lithium salts to form bifunctional electrolytes

capable of reducing the flammability of a battery without negatively impacting performance.

1.5 Works Cited

(1) Bertrand, G. Chemical Reviews 1994, 94, 1161.

(2) Knowles, J. R. Annual Review of Biochemistry 1980, 49, 877.

(3) Quin, L. D. A Guide to Organophosphorus Chemistry; Wiley: New York, N.Y.,

2000.

(4) Chen, F.; Zhao, Q.; Cai, X.; Lv, L.; Lin, W.; Yu, X.; Li, C.; Li, Y.; Xiong, M.;

Wang, X.-G. Canadian Journal of Microbiology 2009, 55, 1328.

(5) Bates, J. I.; Dugal-Tessier, J.; Gates, D. P. Dalton Trans. 2010, 39, 3151.

(6) Orpen, A. G.; Connelly, N. G. Organometallics 1990, 9, 1206.

(7) Crabtree, R. H. In The Organometallic Chemistry of the Transition Metals; John

Wiley & Sons, Inc.: 2005, p 87.

(8) Quin, L. D.; Wiley: New York, N.Y., 2000.

(9) Gilheany, D. G. In The Chemistry of Organophosphorus Compounds; Hartley, F.

R., Ed.; Wiley: New York, 1990; Vol. 2, p 1.

(10) Gilheany, D. G. Chemical Reviews 1994, 94, 1339.

(11) Chesnut, D. B.; Savin, A. Journal of the American Chemical Society 1999, 121,

2335.

(12) McNaught, A. D.; Wilkinson, A. IUPAC. Compendium of Chemical Terminology,

2nd ed. (the "Gold Book"); WileyBlackwell; 2nd Revised edition edition.

(13) Chiang, C. K.; Fincher, C. R., Jr.; Park, Y. W.; Heeger, A. J.; Shirakawa, H.;

Louis, E. J.; Gau, S. C.; MacDiarmid, A. G. Phys. Rev. Lett. 1977, 39, 1098.

(14) Baumgartner, T.; Reau, R. Chem. Rev. (Washington, DC, U. S.) 2006, 106, 4681.

(15) Wright, V. A.; Gates, D. P. Angew. Chem., Int. Ed. 2002, 41, 2389.

(16) Deschamps, E.; Ricard, L.; Mathey, F. Angew. Chem. 1994, 106, 1214.

(17) Mathey, F. Angew. Chem., Int. Ed. 2003, 42, 1578.

(18) Jin, Z.; Lucht, B. L. J. Am. Chem. Soc. 2005, 127, 5586.

(19) Moliton, A.; Hiorns, R. C. Polym. Int. 2004, 53, 1397.

(20) Freund, M. S.; Deore, B. Self-Doped Conducting Polymers, 2007.

(21) Huang, W. S.; Humphrey, B. D.; MacDiarmid, A. G. Journal of the Chemical

Society, Faraday Transactions 1 1986, 82, 2385.

(22) Horrocks, A. R.; Price, D. In Advances in fire retardant materials.; Woodhead

Publishing: Cambridge, England, 2008.

(23) Horrocks, A. R.; Price, D.; Carty, P. In Fire Retardant Materials; Woodhead

Publishing: 2001.

(24) Camino, G.; Costa, L.; Luda di Cortemiglia, M. P. Polymer Degradation and

Stability 1991, 33, 131.

(25) Dasari, A.; Yu, Z.-Z.; Cai, G.-P.; Mai, Y.-W. Progress in Polymer Science 2013,

38, 1357.

(26) Price, D.; Anthony, G.; Carty, P. In Fire Retardant Materials; Harrocks, A. R.,

Price, D., Eds.; CRC Press: Boca Raton, Fl, 2001, p 1.

(27) Horrocks, A. R.; Price, D. In Advances in fire retardant materials.; Woodhead

Publishing: Cambridge, England, 2008.

(28) Lewin, M.; Weil, E. In Fire Retardant Materials; Horrocks, A. R., Price, D., Eds.;

Woodhead Publishing: 2001.

(29) Lu, S.-Y.; Hamerton, I. Progress in Polymer Science 2002, 27, 1661.

(30) Song, Y. H. a. L. In Flame Retardant Polymer Nanocomposites; Morgan, A. B.,

Wilke, C. A., Eds.; John Wiley and Sons: Hoboken, New Jersey, 2007, p 191.

(31) Wang, X.; Yasukawa, E.; Kasuya, S. Journal of The Electrochemical Society

2001, 148, A1058.

(32) Levchik, S. V. In Flame Retardant Polymer Nanocomposites; Morgan, A. B.,

Wilkie, C. A., Eds.; John Wiley and Sons: Hoboken, New Jersey, 2007, p 1.

(33) Lewin, M.; Weil, E. D. In Fire Retardant Materials; Harrocks, A. R., Price, D.,

Eds.; CRC Press: Boca Raton, Fl, 2001, p 31.

(34) Winter, M.; Brodd, R. J. Chemical Reviews 2004, 104, 4245.

(35) Al Hallaj, S.; Maleki, H.; Hong, J. S.; Selman, J. R. Journal of Power Sources

1999, 83, 1.

(36) Xu, K.; Zhang, S.; Allen, J. L.; Jow, T. R. Journal of The Electrochemical Society

2002, 149, A1079.

(37) Padhi, A. K.; Nanjundaswamy, K. S.; Goodenough, J. B. Journal of The

Electrochemical Society 1997, 144, 1188.

(38) Jow, T. R.; Ding, M. S.; Xu, K.; Zhang, S. S.; Allen, J. L.; Amine, K.; Henriksen,

G. L. Journal of Power Sources 2003, 119-121, 343.

(39) Zhuang, G. V.; Xu, K.; Jow, T. R.; Ross, J. P. N. Electrochemical and Solid-State

Letters 2004, 7, A224.

(40) Aurbach, D.; Talyosef, Y.; Markovsky, B.; Markevich, E.; Zinigrad, E.; Asraf, L.;

Gnanaraj, J. S.; Kim, H. J. Electrochim. Acta 2004, 50, 247.

(41) Xu, K. Chemical Reviews 2004, 104, 4303.

Chapter 2: Synthesis and Characterization of Phosphorus Containing Polyanilines

2.1 Introduction

Polyaniline can be synthesized by chemically or electrochemically oxidizing

aniline in an acidic environment.1 The resulting material is a conjugated polymer whose

electronic properties may be controlled by acid/base treatment and oxidation/reduction

chemistry.1,2 Conjugated polymers have received a great deal of attention due to their use

in molecular electronics, sensors, organic light-emitting diodes (OLEDs), and solar

photovoltaics.3-6 Polyaniline is especially interesting due to its ability to conduct

electricity in a manner similar to metals.1,7 Polyaniline is an attractive material due to its

relatively easy synthesis, redox reversibility, low cost of starting materials, and environmental stability. Polyaniline has found use as an anticorrosive when electrodeposited on metals.8-11 Practical and widespread applications of polyaniline have

been hindered by its lack of solubility in common organic solvents and water.4,12,13

Polyaniline’s electronic properties are tunable in two key ways. One is by

varying the oxidation state of the polymer, and the other is through protonic doping.2,3,5,14

The high degree of tunability is due to the fact that polyaniline is a mixed oxidation state

polymer consisting of reduced diamine benzoid and oxidized diimine quinoid units.5,15

There are three readily accessible oxidation states of the polymer polyaniline: fully

reduced leucoemeraldine, fully oxidized pernigraniline, and half oxidized/half reduced

emeraldine base. The emeraldine base may be doped using a Brönsted acid in a non-

redox reaction, resulting in the formation of an organic polymer salt.1 This process can

be seen in Figure 2.1. When this occurs, the imine nitrogens are protonated to form

internal radical cations. These radical cations will distribute throughout the π system of the polymer to form two semiquinone radical cations, a configuration which has been described by Alan MacDiarmid as a polaron metallic state.1,16 This unique type of doping does not change the net number of π electrons in the polymer backbone, but will drastically increase the conductivity of the material.

H N N

N N n H H+ A- H H N N A- A- N N n H H

H H N N A- A- N N n H H

H H N N A- A-

N N n H H

Figure 2.1: Protonic doping of emeraldine base.

Recent investigations into polyaniline have focused on the inclusion of acidic moieties on the structural backbone of polyaniline.17,18 In these compounds, the acidic groups on the molecule can protonate the nitrogen along the polymer backbone, resulting in a “self-doped” polymer. Some examples of previous studies regarding the addition of

acidic functional groups to polyaniline have focused on the addition of carboxylic acid

(chart 1, left), phosphonic acid (chart 2.1, right) and sulfonic acid groups (chart 2.1,

middle) onto the polyaniline backbone.12,17-19 Of particular interest is the work by Chan

(chart 2.1, right), which incorporates phosphonic acid moieties onto benzyl groups along

the polyaniline backbone.18 The phosphonic acid moieties may then be further

deprotonated, “tuning” the molecule’s electronic properties and increasing the solubility

of the polymer in water when ionized. This chapter focuses incorporating phosphorus

containing moieties on the aromatic carbon of the benzene ring to act as source of protons

for self-doping the polymer.

O OH P O

SO3 SO3H H HO O H H N N N H N n n N N N H b H H N SO H SO H 3 3 P a O OH OH OH Poly(aniline-co-3-amino-4-hydroxybenzoic acid) Sulfonated Polyaniline Poly(o-aminobenzylphosphonic acid)

Chart 2.1: Some functionalized polyanilines.

The formation of a polyaniline copolymer is another way to alter the properties of a polyaniline polymer. Polyaniline copolymers made from aniline and various functionalized anilines are well known.19-23 By forming copolymers, the electronic

properties of the final material may be tuned to highlight desirable properties. We have

prepared copolymers designed to modulate the percentage of phosphorus incorporated

into the polymer backbone by varying the ratios of 2-aminophenylphosphonic acid (2.3)

to aniline starting material. Using this technique we are able to exhibit control regarding

the quantity of phosphorus integrated into the final polyaniline material.

2.2 Results and Discussion

2.2.1 Functionalized Monomer

The ortho-phosphorylated aniline 2-aminophenylphosphonic acid (2.3) was

originally synthesized as an antibacterial compound in 1954 by the action of aqueous

ammonia upon 2-bromobenzenephosphonic acid in the presence of copper(I) oxide

(Scheme 2.1).24 The yield of 2.3 via this route is low (40%) and bromobenzenephosphonic acid is not commercially available.

Br O NH3 O P OH Cu2O P O + OH NH3 (aq) OH

2.3 40%

Scheme 2.1: Literature preparation of 2.3.

The initial approach for the synthesis of 2.3 can be seen in Scheme 2.2. In this

method, aniline was first phosphorylated reaction of diethylchlorophosphate in the

presence of triethylamine to form 2.1. The product of this reaction was to be rearranged

using the phospha-Fries rearrangement via LDA to form the phosphonate 2.2. The ethyl

groups attached to phosphonate 2.2 were then to be removed by refluxing in concentrated

hydrochloric acid to form the 2-aminophenyl phosphonic acid.

O P NH HN OEt NH O NH O 2 OEt 2 3 P refluxing P O NEt3 LDA OEt conc. HCl OH OEt O + P OEt THF THF HCl OEt -HCl NEt3 2.1 2.2 2.3

Scheme 2.2: Original plan for the preparation of 2.3.

Compound 2.1 was isolated as a spectroscopically pure yellow solid in good yields (82.5%), however rearrangement of 2.1 into 2.2 did not proceed as expected. Even when an excess of LDA was used, there was no conversion of phosphate to phosphonate.

The reason for this lack of conversion has to do with the mechanism of the phospho-Fries rearrangement.

The driving force behind the phospho-Fries rearrangement is the difference in stabilities of the two intermediates seen in Figure 2.2.25 According to the commonly accepted mechanism of the phospho-Fries rearrangement, LDA will deprotonate the phenyl group at the position ortho to the phosphate group. The aryl-lithium intermediate is stabilized by the electron rich oxygen located on the phosphoryl group as seen in

Figure 2.2, upper right. There is a migration of the phosphoryl moiety from the oxygen atom to the carbon on the ortho position of the aromatic ring, resulting in an intramolecular rearrangement to a more stable lithium alkoxide phosphonate.25

Treatment with a proton source will yield an ortho-hydroxy phosphonate.

O RO OR P P OR O O OR O LDA Li

-78o C

OH O OLi O P OR P OR OR OR

Figure 2.2: Commonly accepted phospho-Fries rearrangement mechanism.

When an analogous route is taken with a phosphorylated aniline

(phosphoramidate) rather than phosphate, conversion to the phosphonate is not observed.

This process can be seen in Figure 2.3. This is likely due to the difficulty producing a dilithiated nitrogen species after deprotonation (Figure 2.3, lower middle). Indeed, phospho-Fries rearrangement attempts on the phosphoramidate quenched with D2O showed a pseudo-pentet when analyzed by 31P NMR spectroscopy, as seen in Figure 2.4, top. The protonated compound exhibits a pseudo-quartet when analyzed by 31P NMR spectroscopy, as seen in Figure 2.4, bottom. This is evidence that the hydrogen attached to the amine group was being replaced by deuterium, which is coupling with the phosphorus through two-bond coupling.

O O O P OR Li P OR D P OR HN N N OR OR D O OR LDA 2

-78o C

LDA X -78o C

RO OR Li P D D O Li Li N N O N O D O Li P OR 2 P OR OR OR

Figure 2.3: Proposed phosphoramidate rearrangement reaction.

Figure 2.4: 31P NMR spectra of the phospho-Fries rearrangement product when

quenched by D2O (top) and 2.1 (bottom).

Since the desired product was not formed via the phospho-Fries rearrangement, an

alternate route was utilized to prepare 2.2. The successful route takes advantage of the

palladium catalyzed coupling of diethyl phosphite with 2-bromoaniline that produces (2-

aminophenyl)phosphonic acid diethyl ester (2.2, Scheme 2.2).26 This route yielded 2.2 as

a yellow oil in high purity and yield (98.4%).

The revised route to 2.3 is seen in Scheme 2.3. Compound 2.2 is refluxed in

concentrated aqueous hydrochloric acid (12 M) to produce compound 2.3 in essentially quantitative yields. Recrystallization from hot water affords spectroscopically pure 2.3 in

89.2% yield as an off white powder.

PPh3 NH2 NH O NH O Pd(OAc)2 2 refluxing 3 Br O P NEt3 P OEt conc. HCl OH + P OEt O OEt EtOH H OEt 2.2 98.4 % 2.3 89.2%

Scheme 2.3: Optimized synthesis of 2.3.

2.2 X-Ray Diffraction Study of 2.3

X-ray quality crystals of 2.3 were grown by vapor diffusion of ethanol into an

aqueous solution of 2.3. The structure of 2.3 was as determined by a single crystal X-ray

diffraction study is shown in Figure 2.5. As this compound contains both acid and base

functional groups, the molecule is zwitterionic (self-protonated). The zwitterionic

character is evidenced by the inequality of the phosphorus-oxygen bond lengths. Two of

P-O bond lengths are essentially equal (1.500(1), 1.501(1) Å), while the third is significantly longer (1.570(1) Å). The two shorter bond distances are consistent with PO multiple bonds (ca 1.5 bond order), whereas the longer distance is consistent with a PO single bond (P-OH group). These value correlate well with the PO bond lengths reported for [NH4][PhPO2OH] (1.494(2), 1.497(2) and 1.580(3)Å) which is close in composition

27 and nature to 2.3. Like the structure of [NH4][PhPO2OH], the crystal structure of 2.3

also reveals an interesting inter- and intramolecular hydrogen bonding network, as seen

in Figure 2.6. Within the structure of 2.3 there is NH•••OP hydrogen bonding, and the

molecules of 2.3 are bridged by intermolecular POH•••OP hydrogen bonds in the solid

state. The structure of [NH4][PhPO2OH] shows intermolecular NH•••OP and POH•••OP

hydrogen bonding in the solid state.

Figure 2.5: Thermal ellipsoid diagram of 2.3 (50% probability).

Figure 2.6: Thermal ellipsoid diagram of three units of 2.3 shows the intermolecular and

intramolecular hydrogen bonds (shown as dotted lines) of the compound in the solid

state. (50% probability).

2.3 Electrochemical Synthesis and Characterization of Polymers

Films of 2.4 were prepared by potential cycling between -0.25 V to +0.95 V vs.

SCE in a saturated solution of 2.3 in 1 M hydrochloric acid as the supporting electrolyte.1,28,29 This process deposited layers of 2.4 with increasing thickness over 70

scans onto the glassy carbon working electrode, as evidenced by the increasing size of the

waves in the cyclic voltammogram seen in Figure 2.7.

0.4

0.2

0.0 Current (mA)

-0.2

0.0 0.5 1.0 Potential (V vs. SCE)

Figure 2.7: Electropolymerization of a saturated solution of 2.3 in 1.0 M aqueous hydrochloric acid on the glassy carbon working electrode with repeated cycling from -0.2

V to 0.95 V vs. SCE over 70 scans.

After 70 cycles, the electrode was removed from the monomer solution. The polymer film on the electrode was washed with 1.0 M hydrochloric acid to remove excess 2.3, and then placed in a 1.0 M hydrochloric acid solution. The film was then analyzed by cyclic voltammetry, the results of which are seen in Figure 2.8. As reported for polyaniline, two oxidation processes are observed.1 The first electrochemical event at

+0.30 V vs. SCE is typical of polyanilines, but the second event at +0.52 V occurs at a much lower potential than is typical (ca +0.80 V).

0.4

0.2

0.0 Current (mA)

-0.2

-0.4 0.0 0.5 1.0 Potential (V vs. SCE)

Figure 2.8: Cyclic voltammograms of a film of 2.4 over ten cycles in 1.0 M aqueous

hydrochloric acid from -0.20 V to +0.95 V vs. SCE.

The transition near +0.8 V for polyaniline is a structural change to pernigraniline, and under aqueous conditions will result in irreversible degradation of the polyaniline into ammonium salts, benzoquinone and hydroquinone as seen in Figure 2.9.16,18,30

Decomposition is not seen with 2.4, as the polymer shows no loss of electroactivity with repeated oxidations to +0.95 V. Oxidative stability past +0.95 V has also been observed in another phosphorylated self-doped polyaniline.18 The likely cause of this oxidative stability is the strong hydrogen bond between the phosphonic acid moieties and the amine nitrogen group, which inhibits the transition from emeraldine salt to pernigraniline.

Scan 1 Scans 2-9 0.10 Scan 10

0.05

0.00 Current (mA)

-0.05

-0.10 -0.5 0.0 0.5 1.0 Potential (V vs. SCE)

Figure 2.9: Degradation of polyaniline film over 10 cycles in 1.0 M aqueous

hydrochloric acid on the glassy carbon working electrode with repeated cycling from -

0.235 V to +0.95 V.

Chemical polymerization and electropolymerization of compound 2.2 was attempted in a manner similar to 2.3, however there was no evidence of polymer formation. The cyclic voltammogram of the oxidation of a saturated solution of 2.2 in 1

M aqueous hydrochloric acid can be seen in Figure 2.10. The cyclic voltammogram

shows compound decomposition at 0.68 V, however there is no increase in baseline

current over the course of 70 scans, which indicates no film or polymer formation.

0.0100

0.0075

0.0050

Current (mA) 0.0025

0.0000

-0.25 0.00 0.25 0.50 0.75 Potential (V vs. SCE)

Figure 2.10: Cyclic voltammogram of a saturated solution of 2.2 in 1.0 M aqueous

hydrochloric acid on the glassy carbon working electrode with repeated cycling from -0.2

V to 0.8 V vs. SCE over 70 scans.

Chemical synthesis of polymers of 2.2 was also unsuccessful. Reaction of a saturated solution of 2.2 with sodium persulfate in 1 M aqueous HCl yielded a viscous red solution uncharacteristic of polyaniline or phosphorylated polyanilines. More work is needed to ascertain the reason why the ethoxy side chains of 2.3 prohibit polymer formation. Our suspicion is the ethoxy groups bound to phosphorus act as a bulky group, sterically protecting the amine. This protection makes head to tail coupling of monomers

more difficult, and therefore polymer formation of 2.2 unfavorable.

2.2.4 Chemical Synthesis and Characterization of Polymers

In order to more fully ascertain the nature of 2.4, gram scale chemical synthesis was undertaken. The polymerization of 2.3 was accomplished by oxidative coupling in an aqueous solution of 3.5 M HCl (Scheme 3) under conditions used for the synthesis of polyaniline.18 Polymer 2.4 was thus isolated as a dark green powder, consistent with a polyaniline in the emeraldine salt oxidation state.1 Elemental analysis of 2.4 indicated the presence of no chlorine, corroborating the self-doped nature (intramolecular proton transfer from the phosphonic acid to the amine functional group) of 2.4. The backbone of

2.4, seen in the idealized polaronic form in Scheme 2.4, contains an unpaired electron and formal positive charge located on the nitrogen atom of the polymer, creating a polaron.

This polaron is likely charge pinned on the nitrogen atom of the polymer, due to the strong hydrogen bond between the phosphonic acid and nitrogen.16

OH O P O H NH3 O N Na2(SO4)2 P OH n O 3.5 M HCl N H P O OH OH 2.3 2.4 65.0%

Scheme 2.4: Chemical synthesis of 2.4.

The solubility of neutral 2.4 is negligible in water and common organic solvents.

Deprotonation of the polymer through the addition of excess ammonia or sodium hydroxide, however, increases the water solublity. Scheme 2.5 outlines the sequential deprotonatation of 2.4 by the addition of increasing amounts (1, 2, and 4 equivalents) of aqueous sodium hydroxide, and shows the idealized structures of the resulting polymers

2.5, 2.6, and 2.7.

Na O O P O H N

N H n P OH 1 O eq. NaOH OH 2.5

OH O Na P O O O H P N O H 2 eq. NaOH N N H n N P H n O OH P O OH OH 2.4 O 4 eq. NaOH Na 2.6

O 2 Na O 2 Na O O P O H P O N N n N N H P P O O O O 2 Na O 2 Na O 2.7

Scheme 2.5: Synthesis of 2.5, 2.6, and 2.7.

Polymers 2.5, 2.6, and 2.7 were analyzed by UV-visible spectroscopy in water, and the collective data is shown in Figure 2.11. The spectra are dominated by an absorption band at 290 nm having a shoulder 406 nm (4.28 eV and 3.05 eV,

31 respectively). The peak at 290 nm can be attributed to the B band πB→π* transition.

The 290nm transition is hypsochromically shifted compared to polyaniline (322 nm) and

sulfonated polyaniline (320 nm).16 This type of shift is seen to a lesser degree with benzyl phosphorylated polyanilines (311 nm), but is much more pronounced in 2.4-2.7.18

A greater hypsochromic shift is likely due to the significant hydrogen bond between the

oxygen of the phosphoryl group and the proton attached to the amine group, which will

stabilize the π system and increase the energetic difference between the πB→π*gap.

There is no shift in absorption wavelength from the 2.4 to the deprotonated polymers,

showing the polymers maintain similar structures and optical properties upon

deprotonation.

Figure 2.11: UV-Vis Spectra of polymers 2.4, 2.5, 2.6 and 2.7; measured in 10-7 M

aqueous solutions.

The shoulder at 409 nm is presumably due to optical transitions of the polysemiquinone backbone structure (polaron band) of the polyaniline.1,32 Surprisingly,

this band is still present in polymers 2.5-2.7 at the same relative intensity as 2.4.

Compounds 2.5-2.7 are deprotonated after reacting with sodium hydroxide, and hence,

the protons which are dope the polyaniline are removed. A decrease the intensity of the

polaron band relative to the quantity of protons removed would be expected, as this is

what is seen with other self-doping phosphorylated polymers, although this is not what is

seen in the specta of 2.5-2.7.16,18 Polymers 2.5-2.7 are unique in that they maintain this band even after all doping protons are removed.

The FTIR spectrum of 2.4 is shown in Figure 2.12, top. In the spectrum, benzoid and quinoid ring stretching can be identified at 1580 cm-1 and 1500 cm-1,

respectively.33,34 Also seen is secondary amine C-N vibrations (1292 cm-1), C-N benzoid

vibrations (1219 cm-1), in plane deformations of the benzoid-NH-benzoid mixed with C-

H deformations (1149 cm-1), and a characteristic PO stretch (1068 cm-1).14,33,34 As the polymer is deprotonated there is a large relative increase in the intensity of the phosphoryl stretch due to the increased ratio of P-O- units to P-O-H units. Two peaks

2- -1 -1 characteristic of PO3 vibrations (1072 cm and 972 cm ) first appear in the spectrum

18 2- for 5, and dominate the spectrum for 2.7. The domination of the spectrum by PO3

vibrations is also seen in the work done by Chan using benzyl substituted phosphorylated

polyaniline rather than phenyl substituted as presented here. As polymers 2.5-2.7 are progressively deprotonated and the phosphoryl peak increases in intensity, there is a relative decrease in the C-N vibrations from 1290 to 1149 cm-1 and a broadening of ring

stretching at 1580 cm-1 and 1500 cm-1. A decrease in the intensity of ring stretching and

C-N vibrations combined with a dominance of PO stretching points to an increased

symmetry among the polymer backbone, with an increase in the polarization surrounding

the already very polar PO bond.

Figure 2.12: Comparison of the FTIR spectra of the progressively deprotonated polymers

2.4-2.7, showing the 2000-500 cm-1 region.

Attempts to find the polydispersity index and average molecular weight of the

polymer were unsuccessful. The characterization of polyaniline and other conducting

polymers by gel permeation chromatography is a controversial topic.35 In solution,

conducting polymers form colloidal solutions which give inaccurate results using size

exclusion chromatography.36 This aggregation is the result of interchain interactions, dopant, and the synthetic conditions used when initially forming the polymer. Polyaniline is especially susceptible to colloidal formation due to its already low solubility in organic solvents combined with the high concentration of hydrogen bonds between nitrogen and hydrogen groups along the polymer backbone. Compound 2.4 gave unrealistically high

molecular weights when analyzed by GPC in N-Methyl-2-pyrrolidone (NMP). Two methods were used in an attempt to disrupt aggregation and determine the polymer properties by GPC. First a 0.10% solution of LiCl in NMP was used as GPC solvent in an attempt to disrupt hydrogen bonding between phosphorus, nitrogen, oxygen and hydrogen groups, however those attempts were unsuccessful. Secondly a 1% solution of m-cresol was added to the polymer solution, however that was also unsuccessful. The high degree of hydrogen bonding along the polymer backbone makes this category of polyaniline extremely difficult to characterize using available methods of size exclusion chromatography.

2.5 Chemical Synthesis of Copolymers 2.8-2.14

Copolymers of 2.3 and aniline were chemically prepared with varying ratios of

2.3 to aniline. Specifically, a series of copolymers were prepared by the copolymerization of mixtures of 2.3 and aniline in ratios ranging of 1:19 to 9:1 (Table

2.1).

OH O Cl P O Cl P H H NH H H NH3 O NH2 N N Na P Na2(SO4))2 a P OH + b a b O 3.5 M HCl N N H H P O OH 2.3 OH 2.8-2.14

Scheme 2.6: Synthesis of copolymers.

The idealized structure for these compounds can be seen in Scheme 2.6. The

yields of copolymers generally increased as the ratio of aniline to 2.3 was increased.

Interpretation of these yields, however, is difficult as the final material isolated may favor

inclusion of aniline in preference to 2.3, especially since the electron-withdrawing ortho- phosphinate in 2.3 would be expected to make it more resistant to oxidation compared to aniline. In order to assess this possibility, Table 2.1 not only lists reaction yields but also lists the minimum amount of monomer 2.3 that must be incorporated based on the final weight of polymer. This number was arrived at by subtracting the amount of aniline starting material from the total weight of the polymer, then dividing by the total weight of the polymer. Table 2.1 also lists the percent phosphorus in the resulting compound as calculated and found by elemental analysis.

Total Total Total Percent Percent Minimum Percent 2.3 Phosphorus Phosphorus Compound Yield Incorporated Starting Calculated Found in 2.3 Material in Compound Compound 2.8 5% 95.1% 6.4% 0.91% 0.87%

2.9 10% 75.6% 20.4% 1.82% 3.12%

2.10 20% 78.4% 0.1% 3.63% 5.45%

2.11 25% 66.8% 30.1% 4.54% 2.90%

2.12 50% 43.6% 37.2% 9.08% 5.36%

2.13 75% 37.6% 66.4% 13.62% 12.90%

2.14 90% 42.7% 89.2% 17.25% 12.91%

2.4 100% 65.0% 100% 18.16% 15.95%

Table 2.1: Yields of colpolymers along with the minimum amount of copolymer

prepared.

We found that when the percentage of 2.3 as a starting material is increased, there is a general increase in the ratio of incorporated phosphorus as found by elemental

analysis. The reduction in yield, however, indicates that indeed monomer 2.3 is less

readily incorporated into the copolymers than aniline. This is likely due to oxidative

stability of 2.3. Since 2.3 is more difficult to oxidize than aniline, less overall 2.3 is introduced into the polymer backbone. Although much more work is needed to understand the loss of yield and to precisely control the final amount phosphorus in the final product, we have thus demonstrated a basic amount of control regarding the incorporation of phosphoryl units along the backbone of a polyaniline polymer.

2.3 Conclusion

The synthesis of 2.3 has been optimized and its molecular structure has been characterized using a single crystal X-ray diffraction study. Polymer 2.4 has been prepared by electrochemical and chemical oxidation. Chemical polymerization is performed in acidic medium using sodium persulfate, and results in a dark green powder.

There is an intramolecular proton transfer from the phosphonic acid moiety to the amine group of the polymer. The resulting polymer is robust to oxidative stress, showing no significant change in electrochemical activity after potential cycling from -0.25 V to

+0.95 V ten times. The neutral polymer is insoluble in water and common inorganic solvents, but deprotonating using base gives water soluble polymers. The progressive deprotonation of 2.4 with 1, 2 and 4 equivalents of sodium hydroxide yields three water soluble polymers with an increasing degree of ionization on the phosphonic acid groups.

Copolymers 2.8-2.14 were prepared using aniline and 2.3 which show the high tunability of this category of compounds. Attempts to polymerize 2.2 by chemical and electrochemical means were unsuccessful. The synthesis of 2.15 was performed, and

holds potential as a new entryway into functionalized polyanilines. The polymers

prepared present new robust forms of highly tunable, self-doped, phosphorus containing polyanilines.

2.7 Experimental

General Considerations

Aniline was distilled prior to use. Tetrahydrofuran was dried over

sodium/benzophenone, distilled, and stored in a nitrogen-filled MBraun Labmaster 130 dry box. Palladium acetate was purchased from Strem Chemicals and used without further purification. All other reagents were used as received from Sigma Aldrich and

Fisher Scientific. 1H and 31P{1H} NMR spectra were recorded using a 400 MHz Varian

Inova spectrometer tuned to 399.7 MHz and 161.8 MHz respectively. 31P{1H} NMR

13 1 spectra were externally referenced to 85% H3PO4. C{ H}NMR spectra were recorded

using a 600 MHz Varian Inova spectrometer tuned to 150.0 MHz. IR spectra were

recorded using a Midac M2000 FTIR. UV-vis spectra were collected on a Shimadzu

UV-1800 Spectrophotometer. Elemental analyses were by Robertson Microlit

Laboratories, Ledgewood, NJ. Elemental analyses for P and Cl were performed by

Midwest Microlab, Indianapolis, IN.

Diethylphenyl phorphoramidate (2.1):

Tetrahydrofuran (200 mL) was added to a 500 mL round bottom flask. Aniline (12.8 mL,

130.6 mmol), diethyl chlorophosphate (20.1 mL, 138.6 mmol) and triethylamine (20.1

mL, 143.3 mmol) were added producing a white cloudy solution. The mixture was

stirred for 14 hours. Diethyl ether (100 mL) and distilled water (100 mL) were added to

the round bottom producing two layers. The organic layer was washed three times with

distilled water. The organic layer was then washed three times with 10% NaOH (aq)

(150 mL), followed by a wash with brine (250 mL). The organic layer was dried with

sodium sulfate, and solvent was removed by rotary evaporation leaving a yellow solid.

The crude solid was recrystallized in THF:Hexanes yielding a yellow solid (24.7 g,

82.5%); mp: 90-94°C.

Figure 2.13: 31P{H} NMR Spectrum of 2.1.

Figure 2.14: 31P NMR Spectrum of 2.1.

Figure 2.15: 1H NMR Spectrum of 2.1.

(2-aminophenyl)phosphonic acid diethyl ester (2.2):

Compound 2.2 was prepared according to literature procedure.26 Palladium acetate (1.53 g, 6.82 mmol), triphenyl phosphine (5.33 g, 20.3 mmol) and 2-bromoaniline (18.6 mL,

171 mmol) were added to a 500 mL three neck round bottom flask equipped with a reflux condenser, inlet adapter, glass stopper, and teflon coated stir bar. The reaction vessel was evacuated and purged with nitrogen three times. Diethyl phosphite (26.4 mL, 205 mmol), triethylamine (35.9 mL, 256 mmol) and ethanol (80 mL) were added to the flask by syringe. The reaction mixture was heated to reflux for 30 hours. After the solution cooled to room temperature, diethyl ether (150 mL) was added to the reaction mixture,

and the solution was filtered through a bed of celite on a glass frit. Solvent was removed

by rotary evaporation, resulting in a yellow solid, which was then dissolved in diethyl

ether (150 mL). The resulting solution was washed with brine (3 x 100 mL) and then

extracted with 1.5 M hydrochloric acid (3 x 150 mL). Aqueous 3 M sodium hydroxide

was added until pH was above 7. The aqueous mixture was washed with diethyl ether (4

x 150 mL), and the organic layers were combined, dried with sodium sulfate, and solvent

was removed by rotary evaporation to yield 38.5 grams of a yellow oil (98.4%). 1H NMR

(400 MHz, CDCl3) δ 7.38 (q, J = 8 Hz, 1H); 7.20 (m, 1H); 6.61(m, 2H); 4.02 (m, 4H);

31 1 1.25 (t, J = 8 Hz, 6H). P{ H} NMR (161 MHz, CDCl3) δ 21.4.

Figure 2.16: 31P{H} NMR Spectrum of 2.2.

Figure 2.17: 1H NMR Spectrum of 2.2.

2-Aminophenylphosphonic acid (2.3)

Compound 2.3 was originally prepared by Doak and Freedman in 195224, but an alternate

synthetic route was performed for this work. A sample of 2.2 (5.08 g, 22.2 mmol) was

added to a 100 mL round bottom flask. Concentrated hydrochloric acid (12 M, 50.0 mL)

was added slowly, and the reaction was refluxed for 17 hours. The solvent was removed

by rotary evaporation resulting in a yellow powder, which was then recrystallized from

hot water to yield 10.8 g of 2.3 as an off white powder (89.2%). mp 195-197°C; 1H NMR

(400 MHz, D2O) 7.63 (q, J = 8 Hz, 1H); 7.43 (t, J = 8 Hz, 1H); 7.36 (t, J = 8 Hz, 1H);

31 7.20 (q, J = 8 Hz, 1H); P{H} NMR (161 MHz, D2O) δ 9.8.

31 Figure 2.18: P{H} NMR Spectrum of 2.3 in D2O.

1 2 2 2 2 4 4 6 6 6 ...... 3 7 7 7 7 7 7 7 7 7 04 15 14 00 00 . . . . . 0 1 1 1 1

7 .5 7 .0 6 .5 6 .0 5 .5 5 .0 4 .5 4 .0 3 .5 3 .0 2 .5 2 .0 1 .5 1 .0 0 .5 0 .0 ppm

Figure 2.19: 1H NMR Spectrum of 2.3.

Chemical Synthesis of Poly(2-aminophenylphosphonic acid) (2.4):

In a 1 L round bottom flask, 2.3 (13.7 g, 85.4 mmol) was dissolved in 323 mL of 3.5 M

HCl and cooled to 0° C. A total of 323 mL of a 0.26 M solution of sodium persulfate in distilled water was added drop wise to the solution of 2.3, and the resulting solution was stirred for 16 hours, producing a green slurry. The green slurry was filtered yielding a green powder. The powder was washed with 1 M HCl (300 mL), ethanol (80 mL) and dried in vacuo for 18 hours yielding 8.7 g of a dark green powder (61%). mp > 300 °C;

FTIR (KBr), 3270, 1586, 1497, 1288, 1214, 1150, 1067, 1000, 930, 904, 825, 756, 547,

-1 493 cm ; Anal. Calcd for (C12H11N2O6P2)n: C, 42.25; H, 3.25; N, 8.21; P, 18.16; Cl, 0.00.

Found: C, 41.03; H, 3.63; N, 6.54; O, 28.15; P, 15.95; Cl, 0.00.

Polymer 2.5:

A sample of 2.4 (0.25 g, 1.5 mmol) was added to a 25 mL round bottom flask. A 0.11 M

sodium hydroxide solution (6.7 mL, 0.73 mmol) was added to the round bottom flask and stirred for 5 minutes. The solvent was removed from the green solution resulting in a black powder, which was dried in vacuo to give 0.25 g of 2.4. FTIR (KBr),3417, 1566,

1496, 1404, 1288, 1219, 1142, 1065, 1033, 895, 548 cm-1.

Polymer 2.6:

A sample of 2.4 (0.25 g, 1.5 mmol) was added to a 50 mL round bottom flask. A 0.11 M

sodium hydroxide solution (13 mL, 1.5 mmol) was added to the round bottom flask and

stirred for 5 minutes. The solvent was removed from the green solution yielding a black

powder, which was dried in vacuo to give 0.25 g of 2.5. FTIR (KBr), 3425, 1589, 1496,

1389, 1288, 1219, 1149, 1064, 964,902, 548 cm-1.

Polymer 2.7:

A sample of 2.4 (0.25 g, 1.5 mmol) was added to a 50 mL round bottom flask. A 0.11 M

sodium hydroxide solution (26. mL, 3.0 mmol) was added to the round bottom flask

making a green solution. The solvent was removed by rotary evaporation yielding a

black powder, which was dried in vacuo to give 0.25 g of 2.6. FTIR (KBr), 3401, 2206,

1635, 1604, 1496, 1389, 1288, 1072, 971, 579 cm-1.

Electrochemical Synthesis of 2.4:

Electrochemical synthesis of 2.4 was performed using a saturated solution of 2.3 in a

conventional 3 electrode glass electrochemical cell with a glassy carbon electrode,

graphite counter electrode, and silver/silver chloride reference electrode in ultrapure

water (Millipore) with 1.0 M hydrochloric acid acting as the supporting electrolyte. The

potential at the working electrode was cycled from -0.25 V to +0.95 V vs. SCE at a rate

of 50 mV/s 70 times producing a film on the working electrode.

Electrochemical Synthesis of Polyaniline:

Polyaniline films were electrochemically prepared in a conventional 3 electrode glass

electrochemical cell with a glassy carbon electrode, graphite counter electrode, and

silver/silver chloride reference electrode in ultrapure water (Millipore) with 1.0 M

hydrochloric acid as the supporting electrolyte. The potential at the working electrode

was cycled from -0.25 V to +0.70 V vs. SCE at a rate of 50 mV/s in a solution of 0.56 M

aniline in 1 M HCl, producing a film on the working electrode.

Copolymerization of 2.3 with Aniline at 1:19 ratio (2.8):

In a 1 L round bottom flask containing a Teflon coated stir bar, aniline (6.4 mL, 70.3

mmol) and 2.3 (0.61 g, 3.8 mmol) were dissolved in 3.5 M HCl (150 mL). In a 125 mL

vial, sodium persulfate (17.7 g, 74.3 mmol) was dissolved in distilled water (150 mL).

The flask containing 2-aminophenylphosphonic acid and aniline was placed in an ice bath. The sodium persulfate solution was added drop wise while stirring, causing the

solution to turn a dark green color. The solution was stirred for 16 hours, producing a green slurry. The slurry was filtered through a glass frit producing a green powder. The solid was washed with ethanol (80 mL) and dried in vacuo for 18 hours yielding a dark green powder (6.84 g, 95.1%). Anal. Calc’d for (C12H10ClN2)a•0.95(C12H11N2O6P2)b•0.05.:

C, 65.01; H, 4.56; N, 12.64; P, 0.91. Found: C, 50.95; H, 4.86; N, 9.47, P, 0.87.

Copolymerization of 2.3 with Aniline at 1:9 ratio (2.9):

Aniline (8.72 g, 93.6 mmol) and 2.3 (1.8092 g, 10.40 mmol) were placed in a 500 mL

Erlenmeyer flask and dissolved in aqueous 3.5 M HCl (200 mL). Sodium persulfate

(24.76 g, 103.99 mmol) was dissolved in water (200 mL) for a 0.52 M solution. The flask containing aniline and 2.3 was placed in an ice water bath and the sodium persulfate solution was slowly added drop-wise by separation funnel. The mixture was filtered and washed with water (3 x 30 mL) and ethanol (2 x 25 mL) yielding a green powder (10.82 g, 75.6%). Anal. Calc’d for (C12H10ClN2)a•0.90(C12H11N2O6P2)b•0.10: C, 63.81; H,4.49; N,

12.40; P, 1.82. Found: C, 67.45; H, 5.16; N, 13.21 , P, 3.12.

Copolymerization of 2.3 with Aniline at 1:4 ratio (2.10):

In a 1 L round bottom flask containing teflon coated stir bar, aniline (5.4 mL, 59.3 mmol) and 2.3 (2.37 g, 14.8 mmol) were dissolved in aqueous 3.5 M HCl (150 mL). In a 125 mL vial, sodium persulfate (17.7 g, 74.3 mmol) was dissolved in distilled water (150 mL). The flask containing 2.3 and aniline was placed in an ice bath. The sodium persulfate was added drop wise while stirring, causing the solution to turn a dark green color. The solution was stirred for 16 hours, forming a green slurry. The slurry was

filtered through a glass frit producing a green powder. The solid was washed with ethanol (80 mL) and dried in vacuo for 18 hours yielding a dark green powder (6.23 g,

78.4%). Anal. Calc’d for (C12H10ClN2)a•0.80(C12H11N2O6P2)b•0.20: C, 61.42; H, 4.35; N,

11.94; P, 3.63. Found: C, 57.99; H, 4.92; N, 12.21; P, 5.45.

Copolymerization of 2.3 with Aniline at 1:3 ratio (2.11):

Aniline (7.90 g, 84.8 mmol) and 2.3 (4.86 g, 28.1 mmol) were placed in a 500 mL

Erlenmeyer flask and dissolved with HCl (2.64 M, 225 mL). Sodium persulfate (26.84 g,

112.7 mmol) was dissolved in water (225 mL) making a 0.50 M solution. The

Erlenmeyer flask was placed in an ice water bath and the sodium persulfate solution was slowly added drop-wise. The mixture was filtered and washed with water (3 x 30 mL) and ethanol (2 x 25 mL) yielding a dark green powder (11.3 g, 66.8%). Anal. Calc’d for

(C12H10ClN2)a•0.75(C12H11N2O6P2)b•0.25: C, 60.22; H, 4.29; N, 11.71; P, 4.54. Found: C,

52.23; H, 4.93; N, 9.42, P, 2.90.

Copolymerization of 2.3 with Aniline at 1:1 ratio (2.12):

Aniline (4.50 g, 48.3 mmol) and 2.3 (8.37 g, 48.4 mmol) were placed in a 500 mL

Erlenmeyer flask and dissolved in aqueous 3.5 M HCl (250 mL). Sodium persulfate

(23.21 g, 97.48 mmol) was dissolved in water (194 mL) making a 0.50 M solution. The

(C12H10ClN2)a•0.50(C12H11N2O6P2)b•0.50: C, 54.23; H, 3.94; N, 10.54; P, 9.08. Found: C,

39.92; H, 4.47; N, 7.22; P, 5.36.

Copolymerization of 2.3 with Aniline at 3:1 ratio (2.13):

Aniline (2.02 g, 21.7 mmol) and 2.3 (10.84 g, 62.6 mmol) were placed in a 500 mL

Erlenmeyer flask and dissolved in aqueous 3.5 M HCl (250 mL). Sodium persulfate

(20.09 g, 84.4 mmol) was dissolved in water (169 mL) making a 0.50 M solution. The

Erlenmeyer flask was placed in an ice water bath and the sodium persulfate solution was

added drop-wise. The mixture was filtered and washed with water (3 x 30 mL) and

ethanol (2 x 25 mL) yielding a dark green powder (6.02 g, 37.6%). Anal. Calc’d for

(C12H10ClN2)a•0.25(C12H11N2O6P2)b•0.75: C, 48.24; H, 3.60; N, 9.38; P, 13.62. Found: C,

41.56; H, 5.06; N, 12.34, P, 12.90.

Copolymerization of 2.3 with Aniline at 9:1 ratio (2.14):

Aniline (0.46 g, 4.9 mmol) and 2.3 (7.72 g, 44.6 mmol) were placed in a 500 mL

Erlenmeyer flask and dissolved in 2.3 M HCl (147 mL). Sodium persulfate (11.826 g,

49.67 mmol) was dissolved in water (99 mL) making a 0.50 M solution. The Erlenmeyer

flask was placed in an ice water bath and the persulfate solution was slowly added drop-

wise. The mixture was filtered and washed with water (3 x 30 mL) and ethanol (2 x 25

mL) yielding a dark green powder (4.27 g, 42.7%). Anal. Calc’d for

(C12H10ClN2)a•0.10(C12H11N2O6P2)b•0.90: C, 43.45; H, 3.32; N, 8.44; P, 17.25. Found: C,

37.02; H, 5.23; N, 12.42; P, 12.91.

Polymerization of 2-aminobenzamide (2.15):

In a 250 mL beaker, 2-aminobenzamide (1.01 g, 7.42 mmol) was dissolved in 3.5 M hydrochloric acid (40.0 mL). In a 250 mL Erlenmeyer flask, sodium persulfate (1.81 g,

7.60 mmol) was dissolved in 3.5 M hydrochloric acid (10.0 mL). The sodium persulfate solution was added dropwise to the 2-aminobenzamide solution. After 17 hours the solution turned a dark green color and had a dark green precipitate. The solution was filtered through a glass frit and washed with hydrochloric acid (50 mL) and distilled water (50 mL). The solid was dried in vacuo giving a dark green powder (0.268 g,

26.7%).

2.8 Works Cited

(1) Huang, W. S.; Humphrey, B. D.; MacDiarmid, A. G. J. Chem. Soc., Faraday Trans. 1

1986, 82, 2385.

(2) Geoffrey, S. In Conductive Electroactive Polymers; CRC Press: 2002.

(3) Heeger, A. J. Synth. Met. 2001, 125, 23.

(4) Gao, Z.; Yang, W.; Wang, J.; Yan, H.; Yao, Y.; Ma, J.; Wang, B.; Zhang, M.; Liu, L.

Electrochim. Acta 2013, 91, 185.

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Masikini, M.; Baker, P.; Iwuoha, E. I. Int. J. Electrochem. Sci. 2012, 7, 11859.

(6) Chiang, C. K.; Druy, M. A.; Gau, S. C.; Heeger, A. J.; Louis, E. J.; MacDiarmid, A. G.;

Park, Y. W.; Shirakawa, H. Journal of the Amercan Chemical Society 1978, 100, 1013.

(7) MacDiarmid, A. G. Angew. Chem., Int. Ed. 2001, 40, 2581.

(8) Zhang, Y. Z.; Luo, H. Q.; Li, N. B. Corrosion Engineering, Science & Technology 2011,

46, 580.

(9) Mrad, M.; Dhouibi, L.; Triki, E. Synth. Met. 2009, 159, 1903.

(10) Sazou, D.; Kourouzidou, M.; Pavlidou, E. Electrochim. Acta 2007, 52, 4385.

(11) Rashid, M.; Rahim, A. A.; Noordin, M. J. Anti-Corrosion Methods and Materials 2011,

58, 131.

(12) Chen, C.; Ding, G.; Zhou, D.; Lu, X. Electrochim. Acta 2013, 97, 112.

(13) Qin, Q.; Zhang, R. Electrochim. Acta 2013, 89, 726.

(14) Kang, E. T.; Neoh, K. G.; Tan, K. L. Prog. Polym. Sci. 1998, 23, 277.

(15) Lu, F. L.; Wudl, F.; Nowak, M.; Heeger, A. J. J. Am. Chem. Soc. 1986, 108, 8311.

(16) Yue, J.; Wang, Z. H.; Cromack, K. R.; Epstein, A. J.; MacDiarmid, A. G. J. Am. Chem.

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(17) S. O. Chan, H.; Ng, S.-C.; M. L. Wong, P.; J. Neuendorf, A.; J. Young, D. Chem.

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(18) Chan, H. S. O.; Ho, P. K. H.; Ng, S. C.; Tan, B. T. G.; Tan, K. L. J. Am. Chem. Soc.

1995, 117, 8517.

(19) Li, Y.; Li, G.; Peng, H.; Chen, K. Mater. Lett. 2011, 65, 1218.

(20) Bilal, S.; Gul, S.; Ali, K.; Shah, A.-u.-H. A. Synth. Met. 2012, 162, 2259.

(21) Milczarek, G. Thin Solid Films 2009, 517, 6100.

(22) Homma, T.; Kondo, M.; Kuwahara, T.; Shimomura, M. Polymer 2012, 53, 223.

(23) Oh, M.; Kim, S. Electrochim. Acta 2012, 78, 279.

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Chapter 3: Synthesis and Characterization of Bifunctional Electrolytes for Lithium-

Ion Batteries

3.1 Introduction

The experimental work presented in this chapter contains the author’s

contribution to published work.1

Lithium-ion batteries (LIBs) have become the battery of choice for portable

electronics and mobile communication devices due to their high energy density and their

lack of a memory effect. As their size scales towards transportation applications, there

have been concerns surrounding their safety in light of an increasing number of well- publicized battery fires.2,3 High energy density LIBs present unique challenges, for a

fully charged battery contains highly energetic and reactive materials in the presence of

flammable components and organic solvents. Catastrophic failures of a LIB often

include violent thermal runaway combined with fire and toxic fumes. It is thus

unsurprising that a number of strategies are actively being pursued to manage the risks

associated with LIBs.4

One of the primary components of LIBs is the electrolyte, which in most commercial LIBs is a solution of LiPF6 in mixtures of organic carbonates, including ethylene carbonate, dimethyl carbonate, and diethyl carbonate.5 While many other

lithium salts have been examined for LIBs, LiPF6 presents a balance for the requirements

of batteries regarding conductivity, dissociation constant, ionic mobility, thermal

stability, anodic stability, and stability towards moisture.6 Of note is the novel salt

lithium bis(oxalato)borate (LiBOB) seen in Chart 3.1,7,8 which has been shown to

improve certain aspects of the solid electrolyte interface (SEI) formed at the LIB battery

anode.9-11

Ph O Ph P O O O O O O O O Li B P Li B MeO Me O O O O O O MeO O Ph P Ph O

LiBOB DMMP FRION 1

Chart 3.1: Promising LIB additives.

One way to reduce the flammability of the electrolyte solution is to add flame retardant compounds to the mixture. A number of studies have shown that addition of organophosphorus(V) compounds, such as dimethyl methylphosphonate (DMMP)12

(Chart 3.1), bring forth desirable protection to systems.13-19 Materials containing the

combination of hydroxyl or alkoxy with an organophosphorus group show significant

flame reduction, due to the formation of polymeric dehydrated phosphoric acid formation

upon combustion.20 However, such additives may have deleterious effects on the

operation of the battery, especially if they are susceptible to reduction at the low

potentials of the anode, which would lead to capacity fading. Additives can also disrupt

formation of a robust SEI. Finally, incorporation of additives to a closed system requires

displacement of vital LIB components, and hence also leads to loss of capacity.

Our research goal is to develop unique lithium salts having multi-functional anions which

incorporate known flame retardant organophosphorus moieties into the anion (Flame

Retardant Ions or FRIONs) of a lithium salt. Our lithium salts are rationally designed

based on maximizing the flame retardant properties of the salt, without impairing the

charge transport capabilities of the electrolyte. Desirable attributes of these bifunctional electrolytes include a low molecular weight, weak coordination to counter ions, low toxicity. They should also promote formation of a robust SEI, be relatively inexpensive, and be easy to synthesize.

3.2 Results and Discussion

3.2.1 Synthesis of Lithium Cyclic Triol Borate Salts

Our first attempts at LIB electrolytes involved lithium cyclic triol borate (CTB) salts. Unpublished data from a previous member of the Protasiewicz group suggested lithium CTB salts may improve the capacity of LIBs after several charge/discharge cycles. Potassium, lithium, and tetraethyl ammonium CTB salts were initially synthesized for use in Suzuki coupling reactions as air and water stable boronic acid replacements.21 Literature preparation of CTB salts involves removing water through azeotropic distillation of a triol and boronic acid to isolate a cyclic intermediate compound. This compound is then treated with potassium hydroxide to form a potassium

CTB salt. Salts formed in this manner include K The synthetic pathway for the preparation of CTBs is shown Scheme 3.1.

OH OH R KOH R HO O R OH R' B K OH Toluene B Toluene B OH - O O - O O 2 H2O R' H2O R' (49-99%) (56-99%)

R = Me, Et R'= Aryl, Alkyl

Scheme 3.1: Literature preparation of CTB Salts.21

We were able to optimize the synthesis of this category of salts using two key

improvements, seen in Scheme 3.2. The first improvement was a solvent free formation

of the cyclic intermediate, and the second improvement was using a base soluble in

organic solvents to deprotonate the intermediate compound. Solvent free intermediate synthesis was achieved by heating a mixture of ethyl- or propyl- triol and boronic acid to

220° C in a nitrogen atmosphere. At this high temperature, both reagents will melt and dehydrate, forming the cyclic intermediate in quantative yields. The intermediate is then dissolved in diethyl ether, lithium t-butoxide is added, and the reaction mixture is stirred overnight. Lithium t-butoxide was chosen for three key reasons: lithium t-butoxide is more soluble in organic solvents than LiOH, it has a relatively high molecular weight which makes accurate measurement easier on the small scale, and finally it will produce t-butanol after protonation, which is soluble in organic solvents and may be removed from the final product by filtration rather than drying as in H2O. The desired lithium

CTB salt product is insoluble in diethyl ether, and will form a white precipitate which

may be collected by filtration. Further work-up beyond drying in vauco is unnecessary.

220oC OH OH 20 min. Et LiOtBu, 16 h Et + HO O Et OH Ph B Li -2 H O Et O OH OH 2 O B O 2 O B O Ph Ph

LiC B 92% (quantatative) Et Ph

Scheme 3.2: Improved synthesis of LiCEtBPh.

Previous preparation of lithium CTB salts for use as battery electrolytes required

long heating times and products required additional steps for purification, typically

multiple recrystallization steps, leading to an overall yield of 47% with a 3 day total

synthesis. Using our optimized route, a high yield of product can be achieved in one day.

This method is also applicable to large scales. Several other lithium CTB salts were prepared as seen in Figure 3.1. LiBMeCPh is included in this list, although previously prepared by Yamamoto et. al. This was done for completeness, as LiBMeCPh was originally prepared as a coopling reagent and is used here as a FRION salt. These salts feature both aromatic and aliphatic groups attached to B; and methyl and ethyl groups at the bicyclic carbon bridgehead.

R O Li O B O R'

LiCRBR'

R, R’ = Me, Me 60% + Me, nBu 22% (K+,, 67%) + + Me, Ph 42% (K +,, 83%; Li+, 57%) + Me, 4-MeOPh 43% (K+,, 34%) + Et, PhPh 92% (NEt4 , 98%) Et, nBuBu 80% Et, CyCy 75% Et, OHOH 62%

Figure 3.1: Prepared lithium CTB salts and their yields. CTBs that have been previously

prepared in the literature21 are shown with their cation and yield in parentheses.

Thermal stability of select CTB salts was determined using thermogravimetric analysis (TGA), as seen in Figure 3.2. A high thermal stability followed by retention of mass in the form of char is desired. CTB salts show some mass loss below 200 °C, followed by decomposition at temperatures above 250 °C. The amount of mass, or char, remaining after decomposition is 16% for LiCMeBPh and 25% for LiCEtBPh. These temperatures are well above the normal operating range of a typical lithium ion battery, and the amount of char formed upon pyrolysis is an excellent starting point for future

work. Following these results we sought to improve the thermal and char properties of

FRION material through the introduction of organophosphorus moieties and a reconfiguration of the basic structure of the FRION.

Figure 3.2: TGA of LiCMeBPh and LiCEtBPh.

3.2.2 Efforts towards Phosphorus Containing Lithium Cyclic Triol Borate Salts

Efforts were made to replace the carbon at the bicyclic bridgehead of lithium

CTBs with a phosphorus atom. A representative phosphorus containing cyclic triol borate (PCTB) target would is shown in Figure 3.3.

O OP Li O B O R

R= Aryl, Alkyl

Figure 3.3: Target lithium PCTB salts.

The proposed synthetic route for the preparation of lithium PCTB salts is shown

in Scheme 3.3. Attempts at phosphorus containing PCTBs started from the

commercially available tetrakis(hydroxymethyl)phosphonium chloride (THPC). Two equivalents of potassium hydroxide are added to an aqueous solution of THPC.

Tris(hydroxymethyl)phosphine oxide (THMPO) is then isolated after removal of solvent and extraction with methanol. THMPO is isolated in quantitative yield as a white powder.

OH OH OH Ph B Li Source 2 KOH OH OH O O P Cl OP OP - H O P OH Li 2 - 2 H O B B - H O OH 2 HO O O O OH OH 2 Ph Ph -O CH2 THPC -KCl THMPO (quantatative)

Scheme 3.3: Proposed synthetic route to phosphorus containing CTBs.

Unfortunately THMPO suffers from lack of solubility in the majority of organic

solvents. Indeed, to our knowledge, THMPO is only soluble in water and methanol.

Several attempts to synthesize the cyclic intermediate compound were performed, but

were all unsuccessful. For a more complete account of these experiments, see Appendix

A. After these unsuccessful attempts a different synthetic strategy was employed to

incorporate phosphorus moieties into anions. The transition was made from using

starting materials with phosphine oxides having three phosphorus carbon bonds (O=PR3)

with hydroxyl groups to attaching phosphinic acid groups (O=P(OH)R2) to borate

centers.

Our group’s first successful foray into bifunctional flame retardant ions (FRIONs)

resulted in the identification of FRION 1, seen in Figure 3.4.22 This FRION combines

the oxalate groups of LiBOB and the flame retardant qualities introduced by the presence

of phosphinate groups. FRION 1 was prepared by the solid-state reaction of boric acid,

diphenylphosphinic acid, oxalic acid, and lithium diphenylphosphinide. This reaction

produced FRION 1 and Li(THF)(Ph2PO2H)-(O2PPh2) in a 3:1 ratio. Purification of

FRION 1 involved extraction with THF followed by crystallization via layering the THF

with pentane to isolate FRION 1 in 19% yield.

TGA showed FRION 1 was stable at temperatures below 94.5 °C. This

temperature is above the standard operating temperature of a lithium-ion battery, but not by a wide margin. The combustion properties of FRION 1 were tested by microcombustion calorimetry (MCC). FRION 1 produced char (26.62% by weight) and

will act as a flame retardant when burned. Heating a 0.015 M solution of FRION 1 to 70

°C for 2 weeks showed no visible decomposition when monitered by 31P NMR

spectroscopy. Unfortunately, FRION 1 suffered from low yields a complicated

purification procedure, limiting its utility as a FRION.

Ph O Ph P O O O Li B O O O Ph P Ph O

FRION 1

Figure 3.4: Initial FRION.

3.2.3 Synthesis of H2-DPC

In order to enhance the formation and stability of FRIONs, we sought utilize a

chelating organophosphorus entity to replace the two phosphinato groups in FRION 1.

We thus examined the use of the tetraethyl (2,3-dihydroxy-1,4-

phenylene)bis(phosphonate) (H2-DPC). The synthetic scheme for the preparation of H2-

DPC can be seen in Scheme 3.4. H2-DPC was previously prepared as an impure fashion by the anionic phospho-Fries rearrangement of 1,2-phenylene tetraethyl bis(phosphate)

23 (3.1). To prepare pure H2-DPC, we began with commercially available 1,2-

dihydroxybenzene (catechol). Catechol was reacted with diethyl chlorophosphate in the

presence of trietylamine to yield compound 3.1. The literature preparation of H2-DPC

uses aqueous ammonium chloride to quench the rearrangement reaction to yield a product

with impurities. Attempts to isolate the rearrangement product from impurities produced

by the reaction proved unsuccessful. Although the reaction products of this reaction

appeared pure by 31P and 1H NMR spectroscopy, the product had a dark red color and

was a viscous oil. Any attempts to use this product in subsequent reactions proved

unsuccessful. We hypothesize the aqueous ammonium chloride quench leads to oxidized

side products such as o-quinone, although the exact mechanism of why this occurs is not

understood.

Changing the aqueous ammonium chloride quench to an aqueous hydrochloric

acid (4 M) quench in the second step of the reaction leads to a significantly more pure

product that is suitable for subsequent use. Typically ammonium chloride is an

acceptable proton source for phospho-Fries rearrangement reaction reactions, however

H2-DPC is more acidic than most aromatic alcohols (vide infra), and benefits from a

stronger proton source (pKa of NH4Cl and HCl: 9.24 and -1.7, respectively). Even with the hydrochloric acid quench, there were still be trace amounts of impurity evidenced by a distinct red color when the reaction was performed on the large scale. Purification of

H2-DPC was achieved by slow evaporation of acetone to yield large white crystals.

O O i. LDA HO OH o HO OH EtO P O O P OEt -78 C, THF O O O NEt3 EtO OEt ii. HCl(aq), RT + 2 P OEt P P Cl - EtO OEt OEt -HCl NEt3 HN(iPr)2 EtO OEt - LiCl

3.1 86.6% H2-DPC 66.5%

Scheme 3.4: Preparation of H2-DPC.

3.2.4 X-Ray Crystallographic Study of H2-DPC

The molecular structure of H2-DPC was verified using single crystal X-ray diffraction, and the results of that study are seen in Figure 3.5. In this crystallographic study the hydrogen atoms were located, and they show both intra- and intermolecular hydrogen bonding from the hydrogen atoms of the alcohol groups to the oxygen atoms phosphoryl groups. Figure 3.6 highlights the inter- and intramolecular hydrogen bonding seen two units of H2-DPC.

Figure 3.5: Molecular structure of H2-DPC in the solid state.

Figure 3.6: Intra- and intermolecular hydrogen bonding (dotted lines) between two

molecules of H2-DPC in the solid state.

3.2.5 Acidity of H2-DPC

H2-DPC was titrated using an aqueous solution of sodium hydroxide (1.0 M), and the pKa was found (5.41, data can be found in the Experimental section). The molecule is relatively acidic when compared to other catechol compounds. The high acidic activity of H2-DPC compound may be attributed to the strong electron withdrawing phosphoryl groups attached to the phenyl ring, which stabilize the negative charge associated with the removal of a proton. For comparison, the pKa of catechol is 9.35.24 Catechols with electron withdrawing groups on the aromatic ring typically have a reduced pKa. For example, 4,5-dichlorocatechol has a pKa of 8.17, and tetrachlorocatechol has a pKa of

24 5.83. The pKa of H2-DPC resembles more closely that of the tetrachlorocatechol than

catechol, experimentally verifying the large electron withdrawing effect the phosphoryl groups have on the electronic properties of the benzene ring.

3.2.6 Synthesis of DPC Based FRIONs

Reaction of two equivalents of H2-DPC with boric acid and LiOtBu in refluxing toluene for 4 hours produced a white precipitate. Filtration and drying yields

Li[B(DPC)2] in 73% yield as an analytically pure white solid as seen in Scheme 3.5. For large scale reactions a Dean-Stark trap was utilized to azeotropically distill water from the reaction mixture. Likewise, reaction of H2-DPC with oxalic acid, boric acid, and

LiOtBu in refluxing toluene for 4 hours produced a similar white precipitate. Filtration and drying yields the asymmetric salt Li[B(DPC)(oxalato)] in 86% yield. During the product design phase, there was concern that Li[B(DPC)(oxalato)] would require further workup, as there was the possibility that LiBOB, and Li[B(DPC)2] may be produced as side products in equivalent ratios. This concern was unfounded however, as 31P NMR spectroscopy showed only a single resonance for Li[B(DPC)(oxalato)]. Large scale preparations of Li[B(DPC)(oxalato)] were performed with the aid of a Dean-Stark trap as well.

To further reduce molecular weight of FRIONs, a lithium tetrafluoroborate analog, LiB[(DPC)2F2] was prepared. Reaction of H2-DPC with BF3 and LiOtBu in toluene was attempted in a manner similar to the previous DPC FRIONs. This reaction failed to produce a precipitate, and removal of the reaction solvent yielded only starting materials. In an alternate synthetic strategy, trimethylsilyl groups were added to the DPC to facilitate fluoride exchange. Trimethylsilyl groups were incorporated onto H2-DPC via the reaction of H2-DPC and two equivalents of Me3SiCl in acetonitrile to generate

25 bis(trimethylsilyl)-DPC in situ. This mixture was then reacted with a solution of LiBF4

in acetonitrile, which formed a white powder. The powder was isolated by filtration and

dried under vacuum yielding Li[B(DPC)F2] as an analytically pure white solid in 54%

yield.

Li[B(DPC)2], Li[B(DPC)(oxalato)], and Li[B(DPC)F2] were characterized by

31 1 multinuclear NMR spectroscopy. The P{ H} NMR spectra (dmso-d6) for Li[B(DPC)2],

Li[B(DPC)(oxalato)], and Li[B(DPC)F2] present resonances at 16.4, 15.2, and 17.7 ppm respectively. Notably, a mixture of Li[B(DPC)2] and Li[B(DPC)(oxalato)] in dmso-d6

showed distinct 31P NMR signals indicating that any ligand exchange or

disproportionation processes are slow on the NMR timescale. Sharp 11B NMR

resonances are also observed at 11.8, 11.8, and 11.5 ppm for Li[B(DPC)2],

Li[B(DPC)(oxalato)], and Li[B(DPC)F2], respectively. These values are shifted slightly upfield compared to that reported for LiBOB (δ 12.2 ppm).7 The 11B NMR spectra

(dmso-d6) for Li[B(DPC)2], Li[B(DPC)(oxalato)], and Li[B(DPC)F2] present

resonances at 16.4, 15.2, and 17.7 ppm respectively. 1H and 13C NMR spectra were

consistent with the expected compounds.

EtO O O OEt P P 0.5 B(OH)3 EtO OEt 0.5 LiOtBu O O Li B ∆, Toluene O O EtO OEt P P EtO O O OEt

Li[B(DPC)2] 73%

B(OH) EtO O 3 P LiOtBu EtO Oxalic acid O O O HO OH Li B O O ∆, Toluene O O P P EtO O EtO OEt P EtO OEt EtO O

Li[B(DPC)(oxalato)] 86% H2-DPC

EtO O P i. 2 TMSCl EtO ii. LiBF4 O F Li B Acetonitrile O F EtO P EtO O

Li[B(DPC)F2] 54%

Scheme 3.5: Synthesis of lithium DPC borate salts.

3.2.7 X-Ray Crystallographic Study of Li[B(DPC)(oxalato)

X-ray quality crystals of Li[B(DPC)(oxalato)] were grown by vapor diffusion of

hexanes into a THF solution of Li[B(DPC)(oxalato)], and the results of a

crystallographic analysis are presented in Figure 3.7. The 1:1 ratio of DPC and oxalato

ligands is rigorously established, and geometries about the boron and lithium centers are

tetrahedral. The lithium ion is coordinated by a phosphoryl oxygen atom (O10) and an

oxalato oxygen atom (O2) of one [B(DPC)(oxalato)] anion, as well as by a phosphoryl

oxygen atom (O7) and an oxalato oxygen atom (O5) of two other [B(DPC)(oxalato)]

anions, which gives rise to a coordination polymer in the solid state. The Li-O distances

span the range from 1.867(1) to 1.989(2) Å, and are within the range of Li-O distances reported for other lithium oxalatoborate and lithium catecholatoborate salts.26-31

Figure 3.7: Molecular structure of Li[B(DPC)(oxalato)] in the solid state (Hydrogen

atoms omitted for clarity).

3.2.8 TGA of DPC FRIONs

A desired feature of these anions a high degree of thermal stability. Each of the new FRIONs were thus examined by thermal gravimetric analysis (TGA). The results of that study are presented in Figure 3.8. Each material is stable to up to 200 °C, but the

Li[B(DPC)F2] shows further stability up to 280°C. TGA confirms the high thermal stability of DPC based FRIONs, which far exceeds the temperature requirements necessary for use in lithium ion batteries.

100

(%) 70

50 Percent Weight

40 Li[B(DPC)2] Li[B(DPC)(oxalato)]

30 Li[B(DPC)F2]

20 100 200 300 400 500 600 700 800 900 Temperature (°C)

Figure 3.8: TGA of lithium borate FRIONs.

3.2.9 Microcombustion Calorimetry of DPC FRIONs

Organophosphorus based flame retardant compounds are well known. One proposed mechanism for their efficacy is based on the fact that when many of these materials undergo combustion a layer of char (polyphosphoric acids) is produced that acts as a thermal and gas barrier.32-35 Further, boron compounds can form a variety of boron- oxide enhanced chars depending upon other neighboring species during thermal decomposition/pyrolysis. Microcombustion calorimetry data (MCC) was performed by

Dr. Alexander Morgan at the Univeristy of Dayton. Data for these salts were obtained for Li[B(DPC)2], Li[B(DPC)(oxalato)], and Li[B(DPC)F2] as well as FRION 1 and

LiBOB, is shown in Table 3.1. From the data in Table 3.1, we can infer that the lithium-

boron complexes are forming high levels of char and showing reduced heat release. As

higher levels of char are formed, less of the electrolyte is available for burning in the

event of a battery fire, and further, depending upon how the battery is penetrated/damaged in a fire, the char may help form seals/caps between layers to slow fire growth in the battery. The LiBOB material shows the lowest total heat release and some of the lowest HRR values, indicating it is the least flammable material tested, and yet it has a low char yield. We hypothesize that this compound has very little carbon present in its structure, and most of that carbon present would decompose in the form of carbon dioxide, which would give off no additional heat. Evolved gas analysis would be needed to confirm this hypothesis, but even without confirmation of LiBOB decomposition chemistry, the low heat release and low char yield is noteworthy. For

Li[B(DPC)2], Li[B(DPC)(oxalato)], and Li[B(DPC)F2], we see higher char yields and a

range of total heat release, with higher char yields being responsible for lower total heat

release as more of the structure is bound up a carbon char rather than as something which

can be pyrolyzed and combusted. These PCFC results show that these new ions have

reduced flammability and should have great potential as flame retardant ions in LIBs.

Average Average HRR Average Char Average HRR Peak Total Heat Compound Peaks Value Yield (%) Temps (°C) Release (W/g) (kJ/g)

158(1), 178(1), 49(1), 82(3), FRION 1 23.62 (0.41) 20.5(0.5) 300(0), 561(1) 4(2), 225(8)

Li[B(DPC)2] 42.20(0.43) 312(2), 446(8) 200(17), 35(3) 12.2(0.3)

Li[B(DPC) 304(1), 327(1), 102(1), 111(1), 49.60(0.05) 8.7(0.1) (Oxalato)] 534(1) 42(1)

LiBOB 18.99(5.17) 360(1), 492(1) 69(2), 9(0) 3.0(0.1)

Table 3.1: MCC results for FRIONs and LiBOB. Standard deviation shown in

parantheses. Samples were tested at 1 °C/sec heating rate

under nitrogen from 75 to 800 °C using method A of ASTM D7309.

3.2.10 DPN Synthesis

Having successfully prepared lithium DPC salts, we sought to extend the π system of the aromatic rings of the DPC ligands by preparing naphthalene derivatives of successful DPC salts. These diphosphinatonapthalene (DPN) systems are a logical extension of DPC systems. Comparison of catechol and naphthalene based lithium borate systems in the literature showed a larger voltage window for lithium naphthalene systems (3.8 V) vs catechol systems (3.6 V).36

The diol 2,3-dihydroxynaphthalene-1,4-(tetraethyl)bis(phosphonate) (H2-DPN)

was prepared in a manner analogous to H2-DPC as seen in Scheme 3.6, however 2,3- dihydroxynapthalene was used as the initial substrate rather than catechol. Reaction of

2,3-dihydroxynapthalene with 2 equivalents of diethylchlorophosphate in the presence of triethylamine produced 2,3-napthelene(tetraethyl)bisphosphate (3.2) in good yields

(75.8%). Rearrangement of 3.2 using LDA in a manner similar to H2-DPC yields white crystals of 2,3-dihydroxynaphthalene-1,4-(tetraethyl)bis(phosphonate) (H2-DPN) after

recrystallization by slow evaporation of acetone.

OEt OEt EtO i. LDA EtO P P O O o -78 C, THF OH O O OH NEt3 ii. HCl(aq), RT + 2 P OEt Cl - OH OEt -HCl NEt3 O HN(iPr)2 OH - P O LiCl P O EtO EtO OEt OEt

3.2 75.8% H2-DPN 39.8%

Scheme 3.6: Preparation of H2-DPN.

3.2.11 Crystallographic Study of H2-DPN

The molecular structure of H2-DPN was confirmed using single crystal X-ray

diffraction, and the results of that study are seen in Figure 3.9. Interestingly, the H2-

DPN appears to only undergo intramolecular hydrogen bonding, compared with the inter-

and intramolecular hydrogen bonding exhibited by H2-DPC (see Figure 3.6). A primary concern of extending the aromatic system is π-stacking, which reduces the solubility of the molecule. In our crystallographic study, the distance between centroids of the aromatic ring is 7.3(1) Å, which is too distant to be considered π stacking. It would appear that the ethoxy groups attached to phosphorous are large enough to disrupt π-

stacking of the molecule in the solid state. Indeed, the packing structure shown in Figure

3.10. There is intramolecular hydrogen bonding between the phosphoryl oxygen and the alcohol attached to the naphthalene ring (Seen in O4-H1-O1 and O5-H2-O6).

Figure 3.9: Molecular structure of H2-DPC. Hydrogen bonding shown in dotted lines.

Non-relevant hydrogen atoms omitted for clarity.

Figure 3.10: Packing diagram of H2-DPN in the solid state. Hydrogens omitted for

clarity.

3.2.12 Synthesis of DPN FRIONs

With successful synthesis of H2-DNP, we set out to prepare Li[B(DPN)2] and

Li[B(DPN)(oxalato)] in a manner analogous to DPC FRIONs, seen in Scheme 3.7.

Reaction of two equivalents of H2-DPN with one equivalent of boric acid and lithium t-

butoxide in refluxing toluene yields the Li[B(DPN)2] salt as an analytically pure white

powder in 78.2% yield after drying. The reaction of H2-DPN with one equivalent of boric acid and one equivalent of oxalic acid did not yield clean Li[B(DPN)(oxalato)], but instead produced a mixture of products.

EtO O O OEt P P 0.5 B(OH)3 EtO OEt 0.5 LiOtBu O O Li B ∆, Toluene O O EtO OEt P P EtO O O OEt OEt EtO Li[B(DPN)2] 73% P O OH

OH P O EtO OEt EtO O H -DPN B(OH)3 P 2 LiOtBu EtO Oxalic acid O O O Li B + Mixture of Products ∆, Toluene O O O EtO P EtO O Li[B(DPN)(oxalato)]

Scheme 3.7: Synthesis of DPN based FRIONs.

31 The P{H} spectrum (dmso-d6) for Li[B(DPN2)] presents a resonance at 16.8

which is similar in range to DPC FRIONs. The 11B NMR chemical shift for

Li[B(DPN2)] is δ 14.3 ppm, and is downfield of LiBOB which has a chemical shift of δ

12.2 ppm.

3.2.13 TGA of Li[B(DPN)2]

The lithium salt Li[B(DPN)2] was studied by TGA, and the results are shown in

Figure 3.11. The Li[B(DPN)2] shows similar thermal stability to lithium DPC salts. The salt is stable at temperatures below 240 °C, well above the operating temperatures of a lithium-ion battery. After decomposition ends, roughly 28% of the material remains solid, indicating a high temperature behavior similar to Li[B(DPC)2].

100

60 Percent Weight (%)

40 Li[B(DPN)2]

20 200 400 600 800 Temperature (oC)

Figure 3.11: TGA of Li[B(DPN)2].

3.2.14 Efforts Toward Other FRION systems

In the course of our investigation, several precursor molecules were prepared that we were unable to convert into lithium salts. Although we have not had success converting the precursors to fully fledged FRIONs, they still may have use as flame retardants in polymers or other systems.

3.2.15 Synthesis of Ethyl-(2-hydroxyphenyl)phosphonic Acid Ester

Our efforts to optimize the desirable traits of FRIONs led us to turn our attention

towards minimizing molecular weight and increasing solubility. One target for this goal

is the FRION seen in Figure 3.12. This FRION is similar to previously made lithium

electrolytes based on salicylic acid lithium borate salts.36 Our goal is to replace the

carbonyl group of salicylic acid with a phosphoric acid group, thus imparting flame

retardant properties. This FRION would utilize the chelate effect, however the molecule

is less symmetric than DPC FRIONs due to the loss of a mirror plane of symmetry along

the boron catechol centers combined with a stereocenter located on the phosphorus

atoms.

O EtO P O O Li B O O P OEt O

R R= H, iPr

Figure 3.12: Target FRIONs.

The reaction scheme for the preparation of ethyl-(2-hydroxyphenyl)phosphonic acid ester (3.5) can be seen in Scheme 3.8. Our approach to the synthesis of the molecule was to first phosphorylate phenol using diethylchlorophosphate in the presence of triethylamine. This well-known reaction yields diethyl(phenyl)phosphate (3.3), which after isolation is rearranged to diethyl(2-hydroxypenyl)phosphonate (3.4) using LDA via the phospho-Fries rearrangement. The ethyl group attached to phosphorus is removed by refluxing 3.4 in a 1 M solution of sodium hydroxide. The removal of only one group is confirmed by NMR spectroscopy, which shows integration for only 2 ethyl hydrogens for

3.5 rather than 4 ethyl hydrogens for 3.4. There is also shift in the chemical shift in the 31

P NMR spectrum from δ 22.8 to 23.5 ppm.

O O P OEt P OEt OH O OH O OH O Cl OEt OEt i. LDA P P NEt3 ii. NH4Cl OEt 1 M NaOH OH OEt OEt -HCl NEt3 - HNiPr - NaOEt - LiCl

3.3 (70-90%) 3.4 (60-90%) 3.5 (77%)

Scheme 3.8: Synthesis of 3.5.

3.2.16 Efforts Toward Ethyl-(2-hydroxyphenyl)phosphonic Acid Ester Based

FRIONs

Compound 3.5 was reacted in toluene with B(OH)3, B(OMe)3, and B(OiPr)3, in a

manner similar to previously made FRIONs, however clean conversion to a FRION was

not seen. After isolation, the reaction appeared to form a complex mixture of products.

The 31P NMR spectrum of these products can be seen in Figure 3.13. Typical 31P chemical shifts for FRIONs are between 15-17 ppm, however the majority of chemical shifts seen in these products are not reasonably close to these compounds.

Figure 3.13: 31P NMR spectrum of reaction products between 3.5, LiOtBu, and

B(OMe)3.

3.2.17 Efforts Toward Biphenol FRIONs

LIB electrolyte salts have been made from lithium bis[2,2'-biphenyldiolato(2-)-

O,O']borate, seen in Figure 3.14. These lithium salts have a very large (4.1 V) voltage window. Even after the salts oxidatively decompose, they still act as charge carriers which expands the voltage window even further.36

O O Li B O O

Figure 3.14: Lithium bis[2,2'-biphenyldiolato(2-)-O,O']borate.

Upon decomposition, lithium bis[2,2'-biphenyldiolato(2-)-O,O']borate forms an ionically conducting polymer which serves to protect further decomposition of the anion.36 Using this structural backbone, we sought to add phosphorus groups in an effort

to make this electrolyte flame retardant. The target for this synthesis is lithium bis[2,2'-

biphenyl(tetraethyl)diphosphinato-diolato(2-)-O,O']borate, seen in Figure 3.15.

O O (EtO)2(O)P P(O)(OEt)2 Li B (EtO)2(O)P O O P(O)(OEt)2

Figure 3.15: Target FRION salt lithium bis[2,2'-biphenyl(tetraethyl)phosphinato-

diolato(2-)-O,O']borate.

Synthesis of 2,2'-dihydroxy-biphenyl(tetraethyl)phosphonate (3.7) began by first

phosphorylating o,o’-biphenol with two equivalents of diethylchlorophosphate in the

presence of an excess of triethylamine, as be seen in Scheme 3.9. This reaction yields

o,o’-biphenyl(tetraethyl)phosphate (3.6). Compound 3.6 is rearranged using two

equivalents of LDA via the phospho-Fries rearrangement, yielding 3.7 as a yellow oil.

O O P OEt P OEt O OH Cl OEt O OEt i. 2 eq. LDA EtO P OH NEt EtO 3 ii. HCl (aq) -HCl NEt - 3 HNiPr OEt - LiCl HO EtO O HO P OEt EtO P O O

3.6 (50.7) 3.7 (58.0)

Scheme 3.9: Synthesis of 2,2'-biphenyl(tetraethyl)diphosphinato-diol.

3.2.18 Efforts Towards Lithium Biphenolphosphonate Borate FRIONs

Compound 3.7, boric acid, and lithium t-butoxide were refluxed in toluene overnight, seen in Scheme 3.10. Water was removed from the reaction mixture using a

Dean-Stark trap in an effort to drive the formation of FRION salts. Upon removal of solvent, a viscous oil was recovered. The mixture was analyzed by 31P NMR spectroscopy which showed several resonances consistent with formation of multiple products as can be seen in Figure 3.16.

O EtO P OH 0.5 B(OH)3 EtO 0.5 LiOtBu Mixture of Products OEt ∆, Toluene HO P OEt O 3.7

Scheme 3.10: Reaction of 3.7 with B(OH)3 and LiOtBu.

Figure 3.16: 31P NMR spectrum of the reaction product of 3.7, boric acid, and lithium t-

butoxide.

3.3 Conclusions

Several novel lithium electrolytes were synthesized and characterized. The synthesis of

lithium CTB salts was optimized to be high yielding and to require no purification

beyond filtration and drying. These salts are thermally stable up to 250 °C although they

produce low amounts of char upon combustion. Phosphorus containing FRIONs

Li[B(DPC)2], Li[B(DPC)oxolato], and Li[B(DPC)F2] were prepared and characterized

by multinuclear NMR spectroscopy. Li[B(DPC)oxolato] was characterized by X-ray crystallography, confirming a 1:1 ratio of DPC to oxalate ligand. TGA and flame testing using MCC shows the DPC based FRION salts are stable at temperatures below 200 °C

and Li[B(DPC)F2] was stable up to 300 °C. When DPC FRION salts do combust, they generate a high percentage of char relative to their starting weight. The prepared salt

Li[B(DPN)2] has an extended π-system and holds potential as a lithium ion battery electrolyte. Several other FRION precursors have been prepared, which may be suitable as flame retardants in other material systems.

3.4 Experimental

Acetonitrile, boric acid, tetrahydrofuran, hexanes and toluene were purchased from

Fisher Scientific. Diethyl chlorophosphate, 1,2-dihydroxybenzene (catechol), 2,3- dihydroxynapthalene, lithium tetrafluoroborate, trimethylsilylchloride triethylamine, diisopropylamine, lithium t-butoxide, and 2.5 M n-butyl lithium in hexanes were purchased from Sigma Aldrich. Oxalic acid was purchased from Acros Organics.

Trimethylolpropane, phenylboronic acid and lithium hydroxide were purified according to Armarego, Wilfred L.F.; Chai, Christina Li Lin (2009). Purification of Laboratory

Chemicals (6th Edition). Elsevier. Air free reactions were performed using standard

Schlenk techniques in a nitrogen atmosphere. When air free techniques were used, tetrahydrofuran and toluene were dried over sodium benzophenone, distilled in a nitrogen atmosphere, and stored in a nitrogen-filled MBraun Labmaster 130 dry box prior to use.

Acetonitrile was dried over calcium hydride, distilled in a nitrogen atmosphere, and stored in a nitrogen-filled MBraun Labmaster 130 dry box prior to use. All other reagents were used without further purification. 1H and 31P{H} NMR data was recorded using a 400 MHz Varian Inova NMR spectrometer tuned to 399.7 and 161.9 MHz respectively. 13C{H} NMR data was recorded using 600 MHz Varian Inova NMR

spectrometer tuned to 150.2 MHz for all other compounds. 11B{H} NMR data was

recorded on a 300 MHz Varian Mercury NMR spectrometer tuned to 96.3 MHz for

11 Li[B(DPC)2], and Li[B(DPC)(oxalato)]. B{H} NMR data was recorded on a 600 MHz

19 Varian Inova NMR spectrometer tuned to 192.6 MHz for Li[B(DPC)F2]. F NMR was

recorded on a 400 MHz Varian Inova NMR spectrometer tuned to 376.3 MHz. 1H and

13 C{H} NMR chemical shifts were internally referenced to trace quantities of CHCl3 and

11 31 DMSO-d5 resonances found in CDCl3 and DMSO-d6, respectively. B{H} and P{H}

NMR chemical shifts were externally referenced to (Et2O)BF3 and H3PO4, respectively.

FTIR spectroscopy data was recorded using a Midac M2000 spectrometer. Melting point

data was measured using a capillary Mel-temp apparatus and was not corrected.

Elemental analyses were by Robertson Microlit Laboratories, Madison, New Jersey.

High resolution mass spectroscopy was recorded at the University of Michigan using an

Agilent Q-TOF HPLC-MS. TGA experiments were performed on a Perkin Elmer DSC 7

using a platinum pan with a N2 flow rate of 40.0 mL/min. The oven temperature was

increased from room temperature to 900 °C with a continuous ramp of 20.00 °C/min.

Experimental data were analyzed and plotted with Origin 8.1 software.

21 Literature Synthesis of LiCEtBPh

Trimethylolpropane (8.56 g, 69.7 mmol) and phenylboronic acid (8.85 g, 66.0 mmol) were added to a 250 mL round bottom flask.. Toluene (100 mL) was added making a clear solution. The solution was brought to reflux for 17 hours, after which it was

returned to room temperature and an aliquot was taken. The reaction was incomplete by

1H NMR and the solution was returned to reflux for 17.5 hours after which an aliquot was

taken. The reaction was complete by 1H NMR. Lithium hydroxide (1.57 g, 65.6 mmol)

was added and the solution was returned to reflux for 17.5 hours, forming a white

precipitate. After the solution returned to room temperature, it was filtered through a

glass frit leaving a white solid (10.32 g, 69.2%). Product was further purified by dissolving in hot butanol, then precipitating with acetone leaving a white solid. This white solid was dried in vacuo at 220 °C. Anal. calc: C, 63.77; H 7.17; N 0.00; Anal.

found trial 1: C, 60.18; H, 7.18; N <.02. Trial 2: C, 60.18; H, 6.99. Trial 3: C, 58.45; H,

7.12.

1 Figure 3.17: H NMR Spectrum of recrystallized, dried, LiCEtBPh in DMSO-d6.

11 Figure 3.18: B NMR Spectrum of of recrystallized, dried, LiCEtBPh in DMSO-d6. NOE

subtraction was used to cancel background from the glass NMR tube.

13 Figure 3.19: C NMR Spectrum of of recrystallized, dried, LiCEtBPh in DMSO-d6.

Monocyclic 1-phenyl-4-ethyl borate

Trimethylolpropane (6.76 g, 50.4 mmol) and phenylboronic acid anhydride (5.24 g, 16.8 mmol) were added to a 100 mL round bottom flask. The flask was placed under a stream of nitrogen and was heated in a sand bath to 220 ºC. Melting and vigorous boiling was observed. After 12 minutes of heating, the reaction mixture was cooled to room temperature. Upon cooling, the reaction mixture changed from an opaque liquid to a white solid (10.55 g, 95.1%).

809 828 847 320 338 357 377 352 853 784 317 334 353 355 411 429 666 670 683 686 690 ...... 0 0 0 1 1 1 1 3 3 4 7 7 7 7 7 7 7 7 7 7 7 13 09 22 24 27 04 09 00 04 ...... 3 2 0 1 4 1 2 1 2

8 .0 7 .5 7 .0 6 .5 6 .0 5 .5 5 .0 4 .5 4 .0 3 .5 3 .0 2 .5 2 .0 1 .5 1 .0 0 .5 ppm

1 Figure 3.20: H NMR Spectrum of LiCEtBPh intermediate.

New Synthesis of LiCEtBPh

Monocyclic 1-phenyl-4-ethyl borate (5.06 g, 23.0 mmol) was added to a 100 mL round

bottom flask. Diethyl ether (60 mL) was added, making a clear solution. Lithium t-

butoxide (1.83 g, 22.9 mmol) was added to the solution, making a white precipitate. The

slurry was stirred for 24 hours. The solution was filtered through a glass frit, and a white

solid was collected. The solid was dried in vacuo for two hours yielding a white powder

(4.80 g, 92.3%).

1 Figure 3.21: H NMR Spectrum of LiCEtBPh in DMSO-d6.

n-Butyl boronic acid:

THF (150 mL) was added to a flame dried 250 mL round bottom flask.

Triisopropylborate (17.3 mL, 75.0 mmol) was added to this flask by syringe. The flask containing the reaction mixture was placed in a dry ice/acetone bath. Butyllithium (2.5

M, 30.0 mL, 75.0 mmol) was added to the flask by glass syringe. The solution was removed from the dry ice/acetone bath and stirred for 17 hours. A 6.0 M solution of aqueous HCl (10 mL) was added to the round bottom flask. The solution was transferred to a 500 mL Erlenmeyer flask and diethyl ether (100 mL) was added. The organic layer was collected. The aqueous layer was washed with diethyl ether (3 x 50 mL). The organic layers were combined and solvent was removed by rotary evaporation leaving an

off white solid. The solid was dried in vacuo, titurated with hexanes (20 mL), and further

dried in vacuo yielding a white powder (4.69 g, 61.3%).

1 Figure 3.22: H NMR Spectrum of n-butylboronic acid in DMSO-d6.

n-Butyl cyclic intermediate:

n-Butylboronic acid (4.15 g, 40.7 mmol) and 1,1,1-trishydroxymethylpropane (5.46 g,

40.7 mmol) were added to a 100 mL round bottom flask. The flask was placed under a stream of nitrogen. The flask containing the reactants was heated to 220 ºC for 5 minutes using a sand bath. After 5 minutes, the flask was cooled to room temperature which yielded a yellow viscous oil (6.26 g, 77.0%).

1 Figure 3.23: H NMR Spectrum of n-butyl cyclic intermediate in DMSO-d6.

LiCEtBnBu:

Cyclic 1-butyl-4-ethyl-4-hydroxymethyl borate (6.26 g, 31.3 mmol) was added to a 100 mL round bottom flask. Diethyl ether (60 mL) was added, making a clear solution.

Lithium t-butoxide (2.506 g, 31.3 mmol) was added to the solution, making a white precipitate. The slurry was stirred for 16 hours. The solution was filtered through a glass frit, and a white solid was collected. The solid was dried in vacuo for two hours yielding a white powder (5.18 g, 80.3%).

1 Figure 3.24: H NMR Spectrum of LiCEtBn-Bu in DMSO-d6.

1,2-phenylene tetraethylbis(phosphate) (3.1) (modified from literature procedure 37)

Catechol (20.0 g, 182 mmol) was dissolved in THF (350 mL) in a 500 mL round bottom flask. Diethylchlorophosphate (63.1 mmol, 437 mmol) and triethylamine (91 mL, 650 mmol) were added forming a white precipitate. The reaction mixture was stirred for 15 hours. Diethyl ether (100 mL) was added and the solution was filtered over a bed of celite on a glass frit. The solvent was removed by rotary evaporation revealing a yellow oil. Diethyl ether (200 mL) was added and the solution was washed three times with a 2

M solution of sodium hydroxide (150 mL each). The organic layer was washed three

times with brine (150 mL each). The organic layer was dried with sodium sulfate and

solvent was removed by rotary evaporation yielding 1 as a yellow oil (60.1 g, 86.6%). 1H

3 NMR (399.7 MHz, CDCl3) δ 1.33 (t, J = 8.0 Hz, 12H), 4.23 (m, 8H), 7.11 (m, J = 4.0

31 Hz, 2H), 7.38 (m, 2H); P{H} NMR (161.9 MHz, CDCl3) δ -6.9.

31 Figure 3.25: P{H} NMR Spectrum of 3.1 in CDCl3.

1 Figure 3.26: H NMR Spectrum of 3.1 in CDCl3.

1,4-tetraethylbis(phosphonate) catechol (H2-DPC) (modified from a previously reported method)37

A 250 mL round bottom flask with THF (40 mL) and diisopropylamine (32.5 mL, 230. mmol) was chilled using a dry ice/acetone bath. A sample of 2.5 M nBuLi in hexanes

(92 mL, 230 mmol) was added by syringe. The mixture was stirred for 30 min. To this mixture was added via cannula a solution of 1,2-phenylene tetraethylbis(phosphate) (20.0 g, 52.3 mmol) in THF (10 mL). The mixture was stirred for 2 hours at dry ice/acetone temperatures, after which the ice/acetone bath was removed and the mixture allowed to warm to room temperature and stirred for another hour. The mixture was then slowly

transferred via cannula to an Erlenmeyer flask containing 4M hydrochloric acid (200 mL). The mixture was extracted three times with methylene chloride (100 mL each).

The combined organic extracts were combined, dried with sodium sulfate, and the solvent was removed by rotary evaporation to yield an off-white oil. The oil, upon standing, yielded white crystals of H2-DPC which were collected and

1 3 dried (13.3 g, 66.5%); m.p. 80-83 ºC. H NMR (399.7 MHz, CDCl3) δ 1.31 (t, JHH = 8

Hz, 12H), 4.10 (m, 8H), 6.91 (m, 2H); 31P{H} NMR δ 20.4.

31 Figure 3.27: P{H} NMR Spectrum of H2-DPC in CDCl3.

100

1 Figure 3.28: H NMR Spectrum of H2-DPC in CDCl3.

101

Titration of H2-DPC

Trial 1 Trial 2

mL 1 M mL 1 M

pH NaOH pH NaOH

4.02 0 3.33 0

4.34 0.2 3.57 0.1

4.68 0.4 3.85 0.2

4.98 0.7 4.17 0.3

5.15 0.9 4.55 0.4

5.41 1.2 4.63 0.5

5.68 1.5 4.69 0.55

5.92 1.8 4.81 0.6

6.27 2.1 4.94 0.74

9.46 2.6 5.05 0.86

9.73 2.8 5.15 0.93

10.08 2.9 5.25 1.02

10.25 3.1 5.35 1.12

10.32 3.3 5.46 1.3

10.42 3.5 5.54 1.4

10.53 3.9 5.63 1.5

10.61 4.2 5.71 1.61

10.68 4.6 5.83 1.72

10.68 4.6 5.95 1.89

6.09 2.01

6.28 2.14

102

6.45 2.3

6.83 2.4

8.23 2.56

8.85 2.58

9.23 2.62

9.61 2.7

9.71 2.76

9.95 2.85

10.14 3

10.22 3.1

10.29 3.2

Li[B(DPC)2]:

Boric acid (0.400 g, 6.47 mmol) and H2-DPC (5.02 g, 13.1 mmol) were dissolved with stirring in toluene (100 mL) in a 250 mL round bottom flask. Upon addition of lithium t-

butoxide (0.0516 g, 6.45 mmol) a white slurry appeared. The slurry was heated to reflux

for 4 hours, then cooled to room temperature. A white precipitate was isolated by

filtration of the mixture through a glass frit The white powder was dried in vacuo to

1 afford Li[B(DPC)2], (3.73 g, 74.3%); m.p. 238-246 °C; H NMR (399.7 MHz, DMSO- d6) δ 1.20 (t, 8 Hz, 24H), 3.99 (m, 3.95-4.04, 16H), 6.92 (dd, J = 8 Hz, 4 Hz, 4H);

13C{H} NMR (150.2 MHz, DMSO-d6) δ 21.3, 66.5, 115.4 (d, J = 180 Hz), 125, 159;

31P{H} NMR (161.9 MHz, DMSO-d6) δ +16.4; 11B{H} (96.3 MHz, DMSO-d6) δ 11.8

(peak width=52 Hz); FTIR (KBr): 5436 (m), 2988 (m), 2931 (w), 2907 (w), 1644 (w),

103

1442 (s), 1398 (m), 1337 (m), 1277 (m), 1236 (m), 1212 (m), 1164 (m), 1091 (s), 1023

(s), 970 (s), 881 (w), 792 (m), 764 (m), 716 (m), 692 (m), 586 (m); Anal. Calcd for

C28H44BLiO16P4: C, 43.18; H, 5.70. Found: C, 42.90; H, 5.26.

31 Figure 3.29: P{H} NMR Spectrum of Li[B(DPC)2] in DMSO-d6.

104

1 Figure 3.30: H NMR Spectrum of Li[B(DPC)2] in DMSO-d6.

105

13 Figure 3.31: C{H} NMR Spectrum of Li[B(DPC)2] in DMSO-d6.

106

11 Figure 3.32: B{H}NMR Spectrum of Li[B(DPC)2] in DMSO-d6.

Li[B(DPC)(oxalato)]:

H2-DPC (5.05 g, 13.2 mmol), boric acid (0.815 g, 13.2 mmol) and oxalic acid (1.19 g,

13.2 mmol) were dissolved in toluene (100 mL) with stirring within a 250 mL round bottom flask. Lithium t-butoxide (1.06 g, 13.2 mmol) and the resulting white slurry was heated to reflux for 4 hours. The mixture was cooled to room temperature, and the white precipitate was isolated by filtration of mixture through a glass frit. The solid was dried to afford Li[B(DPC)(oxalato)] as a white powder (4.98 g, 77.6%). X-ray quality crystals were grown by vapor diffusion of hexanes into THF of Li[B(DPC)(oxalato)]. mp >300

1 3 °C; H NMR (399.7 MHz, DMSO-d6) δ1.21 (t, JHH = 8Hz, 12H), 4.01 (m, 8H), 6.99 (m,

107

13 2H); C{H} NMR (150.2 MHz, DMSO-d6) δ 21.3 (d,JPC = 6 Hz), 66.9 (d, JPC = 5Hz),

117.0 (d, JPC = 180 Hz), 126.3 (p, JPC = 8Hz), 158.3 (d, JPC =15 Hz) 164.0;

31 11 P{H}NMR (161.9 MHz, DMSO-d6); δ 15.2; B{H} (96.3 MHz, DMSO-d6) δ 11.8

(LW1/2 = 66 Hz). High Resolution Mass Spectroscopy: (Neg. Ion ESI) Predicted m/z for

C16H22BO12P2 = 479.0685; found for C16H22BO12P2 = 479.0690.

31 Figure 3.33: P{H} NMR Spectrum of Li[B(DPC)(oxalato)] in DMSO-d6.

108

1 Figure 3.34: H NMR Spectrum of Li[B(DPC)(oxalato)] in DMSO-d6.

109

13 Figure 3.35: C{H} NMR Spectrum of Li[B(DPC)(oxalato)] in DMSO-d6.

110

11 Figure 3.36: B{H}NMR Spectrum of Li[B(DPC)(oxalato)] in DMSO-d6.

Li[B(DPC)F2]:

A solution of H2-DPC (1.50 g, 3.90 mmol) in acetonitrile (25 mL) was prepared in a 50

mL round bottom flask. A solution of lithium tetrafluoroborate (0.363 g, 3.90 mmol) in

acetonitrile (25 mL) was prepared in a separate 100 mL round bottom flask.

Trimethylchlorosilane (1.00 mL, 7.8 mmol) was added to the solution of H2-DPC by

syringe and stirred for 5 minutes. The TMSCl/DPC mixture was transferred to the

lithium tetrafluoroborate solution by cannula. After stirring for 24 hours, a white

precipitate was present. The mixture was filtered through a glass frit, and the solid was

collected and dried in vacuo. Li[B(DPC)F2] was thus isolated as a white powder

3 (0.931g, 54.4%). mp: 252-254 °C. 1H NMR (399.7 MHz, DMSO-d6) δ 1.22 (t, JHH =

111

6.8 Hz, 12H), 3.97 (m, 8H), 6.79 (m, 2H); 13C{H} NMR (150.2 MHz, DMSO-d6) δ

16.20, 61.39, 109.33 (d, JPC = 184.1 Hz), 119.2 (m), 154.63 (d, JPC = 16.5 Hz);

31P{H} NMR (161.9 MHz, DMSO-d6) δ 17.7 (LW1/2 = 169 Hz); 11B{H} (192.6

MHz,DMSO-d6) δ 11.5; 19F NMR (376.3 MHz, DMSO-d6) δ -139.4. Anal. Calcd for

C14H22BF2LiO8P2: C, 38.57; H, 5.09. Found: C, 38.65; H, 5.05.

31 Figure 3.37: P{H} NMR Spectrum of Li[B(DPC)F2] in DMSO-d6.

112

1 Figure 3.38: H NMR Spectrum of Li[B(DPC)F2] in DMSO-d6.

113

13 Figure 3.39: C{H} NMR Spectrum of Li[B(DPC)F2] in DMSO-d6.

114

11 Figure 3.40: B NMR Spectrum of Li[B(DPC)F2] in DMSO-d6.

115

19 Figure 3.41: F NMR Spectrum of Li[B(DPC)F2] in DMSO-d6.

2,3-Napthalene-tetraethyl-bis(phosphate) (3.2)

2,3-dihydroxynapthalene (15.0 g, 43.7 mmol) was added to a 1 L round bottom flask.

THF (400 mL) was added, dissolving the naphthalene and making a clear brown solution.

Diethyl chlorophosphate (30.0 mL, 206 mmol) and triethylamine were added by syringe.

A white precipitate formed upon addition of triethylamine. The reactants were stirred for

18 hours. The solution was filtered through a bed of celite on a glass frit and solvent was removed by rotary evaporation. The remaining mixture was dissolved in diethylether

(200 mL) and washed three times with 1 M sodium hydroxide (75 mL each). A liquid

116

liquid extraction was performed, and the organic layer was collected and dried with sodium sulfate. Solvent was removed by rotary evaporation, yielding 3.2 as a yellow oil

(30.3 g, 75.8%).

31 Figure 3.42: P{H} NMR spectrum of 3.2 in CDCl3.

117

1 Figure 3.43: H NMR spectrum of 3.2 in CDCl3.

2,3-Hydroxy-1,4-tetraethylbis(phosphonate)naphthalene (H2-DPN)

Dry THF (50 mL) was added to a 250 mL round bottom flask. The round bottom flask

was placed in a dry ice/acetone bath and diisopropylamine (16.0 mL, 104 mmol) was

added by syringe. nBuLi (2.5 M, 42 mL, 110 mmol) was added by syringe. The mixture

was stirred for 5 minutes, after which 2,3-Napthalenetetraethylbis(phosphate) (10.0 g,

23.1 mmol) was dissolved in dry THF and added to the flask by cannulae. The mixture was stirred for one hour at -78 °C, after which it was brought to room temperature for 2 hours. The reaction mixture was added to a Erlenmeyer flask containing a saturated solution of ammonium chloride (100 mL) and diethyl ether (100 mL). The mixture was

118

stirred for half an hour. A liquid:liquid extraction was performed and the organic layer was kept. The organic layer was dried with sodium sulfate solvent was removed by rotary evaporation yielding an off white solid. The solid was recrystallized by slow evaporation of a mixture of acetone in water yielding H2-DPN (3.98 g, 39.8%) as white crystals. mp=145-146 °C.

31 Figure 3.44: P{H} NMR spectrum of H2-DPN in CDCl3.

119

1 Figure 3.45: H NMR spectrum of H2-DPN in CDCl3.

Preparation of Li[(DPN)2B]

Boric acid (0.110g, 1.78 mmol), H2-DPN (1.54 g, 3.56 mmol), and lithium t-butoxide

(0.140 g, 1.74 mmol) were added to a 100 mL round bottom flask containing 50 mL of toluene, making a clear solution. The solution was heated to reflux for 16 hours using a

Dean-Stark apparatus, then cooled to room temperature. A precipitate formed upon cooling. The reaction mixture was cooled to room temperature and filtered through a glass frit, yielding a white powder (1.22 g, 78.2%). Anal. Calculated for LiC36H48BO16P4:

C, 49.22; H, 5.51. Anal. found for LiC36H48BO16P4: C, 48.98; H, 5.70.

120

31 Figure 3.46: P{H} NMR of Li[(DPN)2B] in DMSO-d6.

121

1 Figure 3.47: H NMR of Li[(DPN)2B] in DMSO-d6.

122

13 Figure 3.48: C{H} NMR Spectrum for Li[(DPN)2B].

o,o’-Biphenyl(tertraethyl)bisphosphate (3.6):

In a 500 mL round bottom flask, o,o’-Diphenol (10.1 g, 54.2 mmol) was dissolved in

THF (300 mL). Diethylchlorophosphate (15.7 mL, 108.6 mmol) was added by graduated cylinder. Triethylamine (21.0 mL, 151 mmol) was slowly added by graduated cylinder making a white precipitate. The solution was stirred for 17 hours, after which diethylether

(100 mL) was added and the precipitate was filtered off. Solvent was removed by rotary evaporation yielding a yellow oil. The oil was dissolved in diethyl ether (150 mL) and was washed with an aqueous solution of 1 M sodium hydroxide (3 x 100 mL), collected,

123

and dried over sodium sulfate. The solvent was removed by rotary evaporation yielding

3.6 as a clear oil (16.6 g, 50.7%).

31 Figure 3.49: P{H} NMR Spectrum of 3.6 in CDCl3.

124

1 Figure 3.50: H NMR Spectrum of 3.6 in CDCl3.

o,o’dihydroxy-m,m’-(tetraethyl)bisbiphenylphosphonate (3.7)

In a drybox, THF (40 ml and 10 mL, respectively) was added to a 250 mL round bottom flask and 25 mL round bottom flask. The flasks were sealed and removed from the drybox. The 250 mL round bottom flask was placed in a dry ice/acetone bath. Lithium diisopropylamide (2.0 M, 49.0 mL, 4.50 mmol) was added by syringe. Compound 3.6

(10.0 g, 21.8 mmol) was added to the 25 mL round bottom flask. The phosphate solution was added to the LDA solution via cannula, and was stirred for 1 hour. The flask was removed from the dry ice/acetone bath and stirred at room temperature for 2 hours. The reaction mixture was then poured into an Erlenmeyer flask containing acetic acid (2 M,

125

200 mL). A liquid:liquid extraction was performed, and the organic layer was kept. The water layer was washed with methylene chloride (3 x 100 mL). The organic layers were combined, dried with sodium sulfate, and solvent was removed by rotary evaporation yielding a yellow oil. The oil was triturated several times with small amounts of toluene

(5 mL) and dried in vacuo until acetic acid was not visible by 1H NMR, yielding 3.7 as a viscous yellow oil (5.80 g, 58.0%).

31 Figure 3.51: P{H} NMR Spectrum of 3.7 in CDCl3.

126

1 Figure 3.52: H NMR Spectrum of 3.7 in CDCl3.

Ethyl-(2-hydroxyphenyl)phosphonic acid ester (3.5)

Diethyl(phenyl)phosphonate (10.0 g, 43.4 mmol) was placed in a 250 mL round bottom flask. Sodium hydroxide (5M, 80 mL, 400 mmol) was added, dissolving the phosphonate and making an amber color solution. The solution was brought to reflux for 17 hours, after which it was cooled to room temperature. Hydrochloric acid (1 M) was added until the solution was acidic as measured by pH paper. A liquid:liquid extraction was performed using methylene chloride (3 x 100 mL), the organic layer was collected and dried with sodium sulfate. Solvent was removed by rotary evaporation yielding an amber oil, which was triturated with ethanol and dried in vacuo yielding 3.5 as a viscous amber oil (6.8 g, 77%).

127

31 Figure 3.53: P{H} NMR of 3.5 in CDCl3.

128

48 . 52 50 48 46 44 42 26 97 96 94 92 05 04 02 00 98 29 25 27 ...... 1 10 7 7 7 7 7 7 7 6 6 6 6 4 4 4 4 3 1 1 00 03 00 09 13 . . . . . 2 2 2 2 3

11 .0 10 .5 10 .0 9 .5 9 .0 8 .5 8 .0 7 .5 7 .0 6 .5 6 .0 5 .5 5 .0 4 .5 4 .0 3 .5 3 .0 2 .5 2 .0 1 .5 1 .0 0 .5 0 .0 ppm

1 Figure 3.54: H NMR of 3.5 in CDCl3.

In a 100 mL round bottom flask, o,o’dihydroxy-m,m’-(tetraethyl)bisbiphenylphosphonate

(2.56 g, 5.58 mmol) was added. Toluene (50 mL) was added making a clear solution.

Boric acid (.173 g, 2.80 mmol) and lithium t-butoxide (0.224 g, 2.80 mmol) were added making a white slurry. The solution was heated to reflux for (no precipitate after 4 hours)

20 hours after which toluene an aliquot was taken. Hexanes (10 mL) were added to form

crystals of U via layering. First crop yield: 0.127 g.

129

Figure 3.55: 31P{H} NMR Spectrum of U.

130

Figure 3.56: 1H NMR Spectrum of U.

Figure 3.57: Full Molecular structure of a network of a crystal isolated from U.

131

Heat Release Rate Data for FRIONs

The samples were tested with the MCC at 1 °C/sec heating rate under nitrogen from 75 to

800 °C using method A of ASTM D7309 (pyrolysis under nitrogen). Each sample was

run in triplicate to evaluate reproducibility of the flammability measurements. Samples

were tested as received (no additional conditioning).

132

HRR Char Yield HRR Peak Total HR Sample Peak(s) (%) Temp(s) (°C) (kJ/g) Value (W/g)

FRION 1 Trial 1 24.06 157, 177, 300, 561 48, 79, 4, 220 20.1

FRION 1 Trial 2 23.24 159, 177, 300, 561 50, 82, 5, 234 21.0

FRION 1 Trial 3 23.55 158, 179, 300, 560 48, 84, 5, 221 20.3

FRION 1-B Average 23.62 158, 178, 300, 561 49, 82, 4, 225 20.5

Li[B(DPC)2] Trial 1 42.54 309, 455 183, 32 12.5

Li[B(DPC)2] Trial 2 42.34 313, 439 216, 38 11.9

Li[B(DPC)2] Trial 3 41.71 313, 445 202, 34 12.1

Li[B(DPC)2] Average 42.20 312, 446 200, 35 12.2

Li[B(DPC)(Oxalato)] Trial 1 49.65 304, 328, 534 101, 110, 42 8.7

Li[B(DPC)(Oxalato)] Trial 2 49.55 303, 327, 534 102, 110, 43 8.6

Li[B(DPC)(Oxalato)] Trial 3 49.59 304, 327, 535 102, 112, 42 8.8

Li[B(DPC)(Oxalato)] Average 49.60 304, 327, 534 102, 111, 42 8.7

LiBOB Trial 1 24.82 360, 493 71, 9 3.0

LiBOB Trial 2 14.98 361, 492 67, 9 2.9

LiBOB Trial 3 17.17 359, 491 68, 9 3.0

LiBOB Average 18.99 360, 492 69, 9 3.0

Table 3.2: All Data for MCC of FRIONs

133

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136

Appendix A – Attempts to synthesize phosphorus containing CTB

O O OH O HO P OH P - B LiOH Li 3 H2O HO OH O B O OH HO

Scheme A.1: Reaction 4-88.

Reaction 4-88:

Tris(hydroxymethyl)phosphine oxide (0.601 g, 4.29 mmol), boric acid (0.267 g, 4.32 mmol), and lithium hydroxide (0.107 g, 4.67 mmol) were added to a 50 mL round bottom flask. Distilled water (5 mL) was added and the mixture was stirred for 40 hours.

Figure A-1: 31P{H} NMR Spectrum of 4-88.

137

O O OH O HO P OH P - B LiOH Li 3 H2O HO OH O B O OH HO

Scheme A.2: Reaction 4-90.

Reaction 4-90:

Tris(hydroxymethyl)phosphine oxide (0.307 g, 2.19 mmol), boric acid (0.130 g, 2.10 mmol), and lithium hydroxide (0.107 g, 2.40 mmol) were added to a 20 mL vial.

Distilled water (0.98 mL) was added and the mixture was stirred. 7 5 6 . . . 48 44 37

190 170 150 130 110 90 80 70 60 50 40 30 20 10 0 -10 -30 -50 -70 -90 -110 -130 -150 -170 -190 ppm

Figure A-2: 31P{H} NMR Spectrum of 4-90.

138

O O OH O HO P OH P - B NaOH Li 3 H2O HO OH O B O OH HO

Scheme A.3: Reaction 4-91.

Reaction 4-91:

Tris(hydroxymethyl)phosphine oxide (0.311 g, 2.22 mmol), boric acid (0.13 g, 2.09 mmol), and sodium hydroxide (0.101 g, 2.53 mmol) were added to a 20 mL vial.

Distilled water (0.96 mL) was added and the mixture was stirred. 1 6 7 4 7 . . . . . 37 38 38 49 52

190 170 150 130 110 90 80 70 60 50 40 30 20 10 0 -10 -30 -50 -70 -90 -110 -130 -150 -170 -190 ppm

139

Figure A-3: 31P{H} NMR Spectrum of 4-91.

O O OH O HO P OH + - + P - B N OH N 3 H2O HO OH O B O OH HO

Scheme A.4: Reaction 4-88.

Reaction 4-88:

Tris(hydroxymethyl)phosphine oxide (0.320 g, 2.28 mmol), boric acid (0.128 g, 2.06 mmol), and 1.0 M tetrabutylammonium hydroxide in methanol (0.53 mL, 2.04mmol) were added to vial. Distilled water (.90 mL) was added and the mixture was stirred. 6 1 1 7 . . . . 36 38 38 47

190 170 150 130 110 90 80 70 60 50 40 30 20 10 0 -20 -40 -60 -80 -100 -120 -140 -160 -180 ppm

Figure A-4: 31P{H} NMR Spectrum of 4-88.

140

O O OH HO P OH OP LiOH Li + 3 H2O B B HO OH H O O O OH 2 HO

Scheme A.5: Reaction 4-93.

Reaction 4-93:

Tris(hydroxymethyl)phosphine oxide (0.307 g, 2.19 mmol), boric acid (0.135 g, 2.35 mmol), lithium hydroxide (0.0560 g, 2.34 mmol), and distilled water (10. mL) were added to a 20 mL nalgene vial and shaken to dissolve all solids. The solution was added to a PTFE chamber in a bomb reactor. The reactor was sealed and placed in oven at 200

°C for 65 hours with an internal pressure reaching 225 PSI. After cooling to room temperature, the solution was analyzed by 31P NMR.

141

Figure A-5: 31P{H} NMR Spectrum of 4-93.

O O OH HO P OH OP LiOH Li + 3 H2O B B HO OH H O O O OH 2 HO

Scheme A.6: Reaction 4-95.

Reaction 4-95:

Tris(hydroxymethyl)phosphine oxide (0.308 g, 2.20 mmol), boric acid (0.135 g, 2.35 mmol), lithium hydroxide (0.059 g, 2.47 mmol), and distilled water (7. mL) were added

142

to a 20 mL nalgene vial and shaken to dissolve all solids. The solution was added to a

PTFE chamber in a bomb reactor. The reactor was sealed and placed in oven at 105 °C for 24 hours with an internal pressure reaching 34 PSI. After cooling to room temperature, water was removed by evaporation under a stream of nitrogen.

Figure A-6: 31P{H} NMR Spectrum of 4-95.

143

Figure A-7: 1H NMR Spectrum of 4-95.

O O OH HO P OH OP + B + LiOH Li + 3 H2O OH O B O OH H2O

Scheme A.7: Reaction 4-96.

Reaction 4-96:

Tris(hydroxymethyl)phosphine oxide (0.308 g, 2.20 mmol), p-tolylboronic acid (0.135 g,

2.35 mmol), lithium hydroxide (0.059 g, 2.47 mmol), and distilled water (7. mL) were

144

added to a 20 mL nalgene vial and shaken to dissolve all solids. The solution was added to a PTFE chamber in a bomb reactor. The reactor was sealed and placed in oven at 105

°C for 24 hours with an internal pressure reaching 34 PSI. After cooling to room temperature, water was removed by evaporation under a stream of nitrogen.

Figure A-8: 31P{H} NMR Spectrum of 4-96.

145

Figure A-9: 1H NMR Spectrum of 4-96.

O HO OH O HO P OH + + 3 H O B B P O 2 OH O OH

Scheme A.8: Reaction 4-97.

Reaction 4-97:

Tris(hydroxymethyl)phosphine oxide (0.514 g, 3.67 mmol) and phenylboronic acid

(0.442 g, 3.62 mmol) were added to a 10 mL round bottom flask. The flask was then added to a 260°C sand bath for six minutes. After the round bottom was added to sand

146

smoke was observed coming from the round bottom flask. The flask was cooled to room temperature.

Figure A-10: 31P{H} NMR Spectrum of 4-97.

147

Figure A-11: 1H NMR Spectrum of 4-97.

O HO OH O HO P OH + + 3 H O B B P O 2 OH O OH

Scheme A.9: Reaction 4-98.

Reaction 4-98:

Tris(hydroxymethyl)phosphine oxide (0.514 g, 3.67 mmol) and phenylboronic acid

(0.442 g, 3.62 mmol) were added to a 10 mL round bottom flask. The flask was then added to a 65°C sand bath. The temperature was then raised to 110 °C. After five

148

minutes at 110 °C the flask was removed from the heat and allowed to cool to room temperature.

Figure A-12: 31P{H} NMR Spectrum of 4-98.

O O OH HO P OH OP + B + LiOH Li + 3 H2O OH O B O OH H2O

Scheme A.10: Reaction 4-99.

149

Reaction 4-99:

Tris(hydroxymethyl)phosphine oxide (0.308 g, 2.20 mmol), p-tolylboronic acid (0.135 g,

2.35 mmol), and lithium hydroxide (0.059 g, 2.47 mmol) were ground together using a mortar and pestle. The powder was added to a bomb reactor and placed in an oven at

110°C for 14 hours. The reactor was cooled to room temperature leaving an off white solid.

Figure A-13: 31P{H} NMR Spectrum of 4-99.

150

Figure A-13: 1H NMR Spectrum of 4-99.

O O OH O HO P OH P + B LiOH Li 3 H2O HO OH O B O OH HO

Scheme A.11: Reaction 5-03.

Reaction 5-03:

Tris(hydroxymethyl)phosphine oxide (0.657 g, 4.69 mmol), boric acid (0.281 g, 4.55 mmol), lithium hydroxide (0.116 g, 4.86 mmol), and distilled water (1.5 mL) were added

151

to a 20 mL glass vial and shaken to make a white slurry. The slurry was added to a Barr reaction vessel and placed in a 110°C oven for 25 hours. Solvent was removed in vacuo yielding a white powder: (0.743 g, 95%)

Figure A-14: 31P{H} NMR Spectrum of 5-03.

152

Figure A-15: 1H NMR Spectrum of 5-03.

O O F Li + OP HO P OH + Li F B- F + 3 HF B F O O OH F

Scheme A.12: Reaction 5-06.

Reaction 5-06:

Tris(hydroxymethyl)phosphine oxide (.401 g, 2.86 mmol) and lithium tetrafluoroborate

(.269 g, 2.86 mmol) were added to a flame dried 5 mL round bottom flask. Air was removed from the flask by vacuum and backfilled with nitrogen three times. The flask was placed in a 65 °C sand bath for one hour. After the hour had elapsed and no change 153

was observed, the temperature was increased to 180°C for 1.5 hours. The solid was investigated using 31P NMR which showed peaks at 43.5 (starting material) and 37.1

(new peak). The flask was again evacuated and back filled with nitrogen three times and placed in a 160°C sand bath for 17 hours.

Figure A-16: 31P{H} NMR Spectrum of 5-06.

O HO O HO HO P OH P + B + 2 H2O HO MeOH O O OH B

154

Scheme A.13: Reaction 5-10.

Reaction 5-10:

Tris(hydroxymethyl)phosphine oxide (0.615 g, 4.65 mmol) and p-tolylboronic acid

(0.5425 g, 3.99mmol) were added to a 100 mL round bottom flask. Methanol (40 mL) was added making a clear solution. The solution was brought to reflux for 17 hours.

Figure A-17: 31P{H} NMR Spectrum of 5-10.

O HO OH O HO P OH + + 2 H O B B P O 2 OH O OH 155

Scheme A.14: Reaction 5-11.

Reaction 5-11:

Tris(hydroxymethyl)phosphine oxide (0.164 g, 1.17 mmol) and phenylboronic acid (.148 g, 1.21 mmol) were added to a 50 mL round bottom schlenk flask. The flask was evacuated and backfilled with nitrogen three times. The flask was placed in a 230 ºC sand bath for 12 minutes. No reaction was observed, but the stir bar did stop as the mixture came together. The flask was cooled to room temperature, and removed from nitrogen.

Figure A-18: 31P{H} NMR Spectrum of 5-11.

156

O HO OH O HO P OH + + 2 H O B B P O 2 OH O OH

Scheme A.15: Reaction 5-13.

Reaction 5-13:

Tris(hydroxymethyl)phosphine oxide (3.13 g, 22.3 mmol) and phenylboronic acid (02.82 g, 23.2 mmol) were added to a 250 mL round bottom flask. Methanol (100 mL) was added making a clear solution. The solution was brought to reflux for five hours, after which an aliquot was taken. The solution was then returned to reflux for 18 hours. The solution was then returned to room temperature and solvent was removed by rotary

evaporation leaving a white solid (4.74 g).

157

Figure A-19: 31P{H} NMR Spectrum of aliquot 1 of 5-13.

158

Figure A-20: 31P{H} NMR Spectrum of final product of 5-13.

159

Figure A-21: 1H NMR Spectrum of final product 5-13.

O HO O HO HO P OH P + B + 2 H2O HO MeOH O O OH B

Scheme A.16: Reaction 5-14.

Reaction 5-14:

160

Tris(hydroxymethyl)phosphine oxide (.310 g, 2.21 mmol) and phenylboronic acid (.402 g, 3.30 mmol) were added to a 50 mL round bottom flask. Methanol (25 mL) was added making a clear solution. The solution was brought to reflux for 17 hours. Solvent was removed by rotary evaporation leaving a white solid (.59 g). The solid was analyzed by

31P NMR. Methanol (25 mL) was added to the round bottom flask and the solution was brought to reflux for 65 hours.

Figure A-22: 31P{H} NMR Spectrum of 5-14.

161

O HO O HO HO P OH P + B + 2 H2O HO MeOH O O OH B

Scheme A.17: Reaction 5-15.

Reaction 5-15:

Tris(hydroxymethyl)phosphine oxide (.305 g, 2.18 mmol) and phenylboronic acid (.553 g, 4.53 mmol) were added to a 50 mL round bottom flask. Methanol (25 mL) was added making a clear solution. The solution was brought to reflux for 17 hours. Solvent was removed by rotary evaporation leaving a white solid . The solid was analyzed by 31P

NMR. Methanol (25 mL) was added to the round bottom flask and the solution was brought to reflux for 65 hours.

162

Figure A-23: 31P{H} NMR Spectrum of 5-15.

O HO O HO HO P OH P + B + 2 H2O HO MeOH O O OH B

Scheme A.18: Reaction 5-16 through 5-19.

Reaction 5-16 through 5-19:

163

Tris(hydroxymethyl)phosphine oxide (TMPO) and phenylboronic acid (PBA) were added to a 50 mL round bottom flask. Methanol (25 mL) was added making a clear solution.

The solution was brought to reflux for 16 hours. Solvent was removed by rotary evaporation leaving a white solid. The solid was analyzed by 31P NMR.

Reaction # PBA TMPO PBA:TMPO 31P

.235 g .264 g 5-16 1:1 48.1, 42.6, 35.5 1.92 mmol 1.88 mmol

.347 g .264 g 5-17 1.5:1 48.1, 42.5, 35.4 2.85 mmol 1.88 mmol

.462 g .259 g 5-18 2:1 48.1, 42.5, 34.7 3.79 mmol 1.85 mmol

1.07 g .247 g 5-19 5:1 47.6, 41.3, 35.4 8.78 mmol 1.76

164

Figure A-24: 31P{H} NMR Spectrum of 5-16.

165

Figure A-25: 31P{H} NMR Spectrum of 5-17.

166

Figure A-26: 31P{H} NMR Spectrum of 5-18.

167

Figure A-27: 31P{H} NMR Spectrum of 5-19.

168

Figure A-28: 1H NMR Spectrum of 5-19.

O HO O HO HO P OH P + B + 2 H2O HO O O OH Toluene B

Scheme A.19: Reaction 5-25.

Reaction 5-25:

Tris(hydroxymethyl)phosphine oxide (0.25 g, 1.8 mmol) and phenylboronic acid (0.24 g, were added to a 50 mL round bottom flask. Toluene (25 mL) was added making slurry.

169

A Dean Stark apparatus was attached to the flask. The flask was sealed with a septa and placed under nitrogen. The slurry was heated to reflux for 16 hours, after which the solvent returned to room temperature. A white precipitate was observed which was collected by filtration on a glass frit.

Figure A-29: 31P{H} NMR Spectrum of 5-25.

170

Figure A-30: 1H NMR Spectrum of 5-25.

171

Appendix B – Efforts towards Novel 1,3-Benzoxaphospholes and Use as Ligands

B.1 Synthesis of a Novel 1,3-Oxaphosphole

OH N O S + Cl THF P PH2 S - Anilinium Chloride B.1

Scheme B.1: Synthesis of B.1.

2-Thiophene-1,3-benzoxaphosphole (B.1):

In a drybox, 2-phosphinophenol (1.52 g, 7.68 mmol) and a stir bar were added to a

100mL round bottom flask. To the flask, approximately 50 mL of THF was added and

the flask was sealed and removed from the drybox. N-phenylthiophene imidoyl chloride

(2.40 g, 10.8 mmol) was added to the round bottom flask by syringe, turning the solution brown. The flask was equipped with a reflux condenser and brought to reflux for 48 hours. Solvent was removed in vacuo and the flask was taken into the drybox. Hexanes

(50 mL) was added to the orange solid forming a slurry, which was stirred for 72 hours.

The slurry was filtered with a glass frit, producing a bright yellow solution. The solution was removed from the drybox, and washed successively with degassed solutions of 10%

aqueous NaOH, 10% aqueous H2SO4 and distilled water. The organic layer was dried with sodium sulfate, solvent was removed in vacuo, and the flask was taken into the drybox. The solid was dissolved in hexanes and the solution was filtered through celite , and then filtered through basic alumina. Solvent was removed in vacuo to produce a yellow solid (0.242g, 9%). mp:49-52 °C.

172

Figure B.1: 31P{H} NMR spectrum of B.1

173

Figure B.2: 1H NMR spectrum of B.1

174

Figure B.3: Aromatic Region of 1H NMR spectrum of B.1

175

Figure B.4: 13C{H} NMR Spectrum of B.1

B.2 Efforts Towards Using 1,3-Benzoxaphospholes as Ligands

O S S O P + Au + CH Cl Au P Cl 2 2 Cl

Scheme B.2: Reaction 1-89.

Reaction 1-89:

Gold (I) chloride (tht) (0.0411 g, 0.1282 mmol) was dissolved in methylene chloride (2 mL) making a clear solution. This solution was transferred by pipet to a 5 mL round

176

bottom flask containing phenyl oxaphosphole (0.0270 g, 0.1273 mmol). The bright

yellow mixture was stirred for 30 minutes, turing the solution a red/brown color. Solvent

was removed by vacuum. Hexanes (2 mL) was added to the round bottom and the slurry

was cooled to -37 °C for 12 hours. The slurry was filtered with a glass frit, collected, and dried in vacuo.

Figure B.5: 31P{H} NMR Spectrum of reaction 1-89.

177

O Cl O + S Au X + P S P Au Cl

Cl P O O P Cl B.2

Scheme B.3: Synthesis of B.2.

B.2:

In the drybox, 2-phenyl-5-isopropyl-1,3-benzoxaphosphole (0.019 g, 0.076 mmol) was

placed in a 25 mL round bottomed flask, and dissolved with methylene chloride (1 mL).

AuCl(tht) (0.025 g, 0.078 mmol) was placed in a 25 mL round bottomed flask and

dissolved with methylene chloride (1 mL). The oxaphosphole solution was added

dropwise to the round bottom containing the AuCl(tht). The mixture was stirred for 20

minutes, then solvent was removed in vacuo, producing a red solid. CDCl3 (1 mL) was added creating a red slurry, which was filtered through celite to remove red residue. 1H

and 31P NMR were taken. After NMR, the NMR tube was brought back into the drybox.

The solution was decanted into a small shell vial. Crystals were attempted to be grown

by slow evaporation, but did not form. Crystals were grown by vapor diffusion of

hexanes into toluene.

178

Figure B.6: Molecular structure of B.2. Hydrogen atoms omitted for clarity.

179

Appendix C – Crystal Structure Determination and Data

Table C.1: Crystal data and structure refinement for H2-DPC.

Compound H2-DPC

Empirical formula C14 H24 O8 P2

Formula weight 382.27

Temperature 100(2) K

Wavelength 1.54178 Å

Crystal system Orthorhombic

Space group Pca2(1)

Unit cell dimensions a = 10.2389(2) Å α= 90°

b = 12.9430(3) Å β= 90°

c = 13.8647(3) Å γ = 90°

Volume 1837.38(7) Å3

Z 4

Density (calculated) 1.382 g/cm3

180

Absorption coefficient 2.496 mm-1

F(000) 808

Crystal size 0.33 x 0.30 x 0.22 mm3

Theta range for data collection 5.51 to 68.16°

Index ranges -12<=h<=12, -15<=k<=15, -16<=l<=14

Reflections collected 11723

Independent reflections 2951 [R(int) = 0.0270]

Completeness to theta = 66.00° 99.2 %

Absorption correction Multi-scan

Refinement method Full-matrix least-squares on F2

Data / restraints / parameters 2951 / 4 / 229

Goodness-of-fit on F2 1.042

Final R indices [I>2sigma(I)] R1 = 0.0468, wR2 = 0.1327

R indices (all data) R1 = 0.0476, wR2 = 0.1346

Absolute structure parameter 0.51(3)

Largest diff. peak and hole 0.412 and -0.379 e Å-3

Table C.2: Atomic coordinates (x 104) and equivalent isotropic displacement parameters

2 3 (Å x 10 ) for H2-DPC. U(eq) is defined as one third of the trace of the orthogonalized Uij

tensor.

______

x y z U(eq)

______

P(1) 7602(1) 7371(1) 1526(1) 38(1)

181

P(2) 2650(1) 7623(1) -1243(1) 34(1)

O(1) 8469(2) 8360(2) 1374(2) 49(1)

O(2) 1797(2) 8562(2) -933(2) 49(1)

O(3) 8449(2) 6495(2) 1073(2) 52(1)

O(4) 4723(3) 7376(2) 2108(2) 47(1)

O(5) 2642(2) 7513(2) 921(2) 44(1)

O(6) 1759(2) 6663(2) -1025(2) 41(1)

O(7) 3120(3) 7683(2) -2247(2) 46(1)

O(8) 7191(3) 7230(2) 2537(2) 56(1)

C(1) 7162(7) 9946(5) 1563(6) 151(4)

C(2) 8287(5) 9275(3) 1948(4) 83(1)

C(3) 6208(3) 7434(2) 751(2) 31(1)

C(4) 4980(3) 7448(2) 1157(3) 33(1)

C(5) 3858(3) 7523(2) 559(2) 30(1)

C(6) 4019(3) 7576(2) -447(2) 32(1)

C(7) 490(3) 8543(3) -567(3) 63(1)

C(8) -174(5) 9500(4) -794(5) 107(2)

C(9) 10216(4) 5324(4) 1136(4) 81(1)

C(10) 9762(4) 6294(3) 1430(5) 83(2)

C(11) 1938(4) 5683(3) -1518(3) 61(1)

C(12) 2983(5) 5064(4) -1085(4) 86(1)

C(13) 5277(3) 7571(2) -830(2) 36(1)

C(14) 6363(3) 7506(2) -245(3) 37(1)

182

Table C.3: Bond lengths [Å] and angles [°] for H2-DPC.

______

P(1)-O(8) 1.475(3)

P(1)-O(3) 1.560(3)

P(1)-O(1) 1.572(2)

P(1)-C(3) 1.788(3)

P(2)-O(7) 1.474(3)

P(2)-O(2) 1.557(2)

P(2)-O(6) 1.572(2)

P(2)-C(6) 1.784(3)

O(1)-C(2) 1.439(5)

O(2)-C(7) 1.431(4)

O(3)-C(10) 1.455(4)

O(4)-C(4) 1.347(4)

O(5)-C(5) 1.342(4)

O(6)-C(11) 1.453(4)

C(1)-C(2) 1.5381(10)

C(3)-C(4) 1.378(5)

C(3)-C(14) 1.393(5)

C(4)-C(5) 1.420(5)

C(5)-C(6) 1.406(5)

C(6)-C(13) 1.394(5)

183

C(7)-C(8) 1.447(6)

C(9)-C(10) 1.398(6)

C(11)-C(12) 1.466(6)

C(13)-C(14) 1.380(5)

O(8)-P(1)-O(3) 116.83(17)

O(8)-P(1)-O(1) 112.87(16)

O(3)-P(1)-O(1) 102.93(15)

O(8)-P(1)-C(3) 110.44(15)

O(3)-P(1)-C(3) 103.61(13)

O(1)-P(1)-C(3) 109.48(14)

O(7)-P(2)-O(2) 113.74(15)

O(7)-P(2)-O(6) 114.38(14)

O(2)-P(2)-O(6) 103.75(13)

O(7)-P(2)-C(6) 109.25(15)

O(2)-P(2)-C(6) 107.26(13)

O(6)-P(2)-C(6) 108.03(13)

C(2)-O(1)-P(1) 121.6(3)

C(7)-O(2)-P(2) 127.6(2)

C(10)-O(3)-P(1) 120.5(3)

C(11)-O(6)-P(2) 121.8(2)

O(1)-C(2)-C(1) 111.7(4)

C(4)-C(3)-C(14) 120.5(3)

C(4)-C(3)-P(1) 118.9(2)

184

C(14)-C(3)-P(1) 120.5(3)

O(4)-C(4)-C(3) 125.2(3)

O(4)-C(4)-C(5) 114.8(3)

C(3)-C(4)-C(5) 120.0(3)

O(5)-C(5)-C(6) 118.7(3)

O(5)-C(5)-C(4) 122.1(3)

C(6)-C(5)-C(4) 119.2(3)

C(13)-C(6)-C(5) 119.1(3)

C(13)-C(6)-P(2) 119.4(2)

C(5)-C(6)-P(2) 121.6(2)

O(2)-C(7)-C(8) 110.4(4)

C(9)-C(10)-O(3) 111.7(4)

O(6)-C(11)-C(12) 112.1(3)

C(14)-C(13)-C(6) 121.4(3)

C(13)-C(14)-C(3) 119.7(3)

______

2 3 Table C.4: Anisotropic displacement parameters (Å x 10 ) for H2-DPC. The anisotropic

displacement factor exponent takes the form: -2π2[ h2 a*2 U11 + ... + 2 h k a* b* U12]

______

U11 U22 U33 U23 U13 U12

______

P(1) 27(1) 50(1) 38(1) 0(1) -10(1) -3(1)

P(2) 26(1) 53(1) 23(1) 1(1) -4(1) 1(1)

185

O(1) 36(1) 58(1) 52(2) -8(1) -5(1) -8(1)

O(2) 36(1) 57(1) 53(2) 4(1) -2(1) 6(1)

O(3) 33(1) 52(1) 70(2) -8(1) -14(1) 2(1)

O(4) 33(1) 89(2) 20(1) 5(1) -3(1) -3(1)

O(5) 25(1) 84(2) 23(1) -2(1) 1(1) -2(1)

O(6) 34(1) 55(1) 34(1) -3(1) -2(1) -4(1)

O(7) 37(1) 78(2) 22(1) 3(1) -5(1) -2(1)

O(8) 39(1) 90(2) 38(2) 10(1) -17(1) -6(1)

C(1) 276(12) 83(4) 94(5) -8(4) -6(6) 35(6)

C(2) 110(4) 61(2) 78(3) -15(2) -6(3) -21(2)

C(3) 26(1) 40(1) 29(2) 0(1) -5(1) -3(1)

C(4) 31(2) 42(1) 28(2) 4(1) -3(1) -4(1)

C(5) 23(2) 47(2) 21(1) 0(1) -1(1) -2(1)

C(6) 28(2) 45(2) 24(2) -1(1) -3(1) -1(1)

C(7) 47(2) 74(2) 67(2) -3(2) 10(2) 12(2)

C(8) 70(3) 126(5) 127(5) 44(4) 32(3) 47(3)

C(9) 60(2) 87(3) 96(4) -7(3) -14(2) 25(2)

C(10) 44(2) 66(2) 140(5) -13(3) -38(2) 12(2)

C(11) 73(2) 63(2) 46(2) -11(2) -9(2) -7(2)

C(12) 96(3) 65(2) 96(4) -10(3) -4(3) 13(2)

C(13) 33(2) 53(2) 23(2) 0(1) 4(1) -1(1)

C(14) 25(2) 53(2) 33(2) -2(1) -1(1) -3(1)

186

______

Table C.5: Hydrogen coordinates (x 104) and isotropic displacement parameters (Å2 x

3 10 ) for H2-DPC.

______

x y z U(eq)

______

H(1A) 7055 10554 1978 226

H(1B) 6352 9543 1562 226

H(1C) 7362 10170 904 226

H(2A) 9104 9685 1946 99

H(2B) 8098 9074 2622 99

H(7A) 509 8444 140 75

H(7B) 9 7956 -856 75

H(8A) -118 9631 -1489 161

H(8B) 239 10070 -443 161

H(8C) -1093 9447 -603 161

H(9A) 9991 5213 457 122

H(9B) 9808 4786 1532 122

H(9C) 11166 5295 1215 122

H(10A) 10361 6835 1188 100

H(10B) 9760 6327 2143 100

H(11A) 2149 5815 -2204 73

H(11B) 1111 5287 -1495 73

187

H(12A) 2711 4830 -443 129

H(12B) 3774 5486 -1026 129

H(12C) 3164 4464 -1494 129

H(13) 5389 7613 -1509 43

H(14) 7213 7510 -519 45

H(5X) 2120(60) 7610(40) 1440(30) 110(20)

H(4X) 5400(40) 7030(50) 2360(60) 150(30)

Table C.6: Crystal data and structure refinement for Li[B(DPC)(Oxalato)].

Compound Name Li[B(DPC)(Oxalato)]

Empirical formula C16 H22 B Li O12 P2

Formula weight 486.03

188

Temperature 100(2) K

Wavelength 0.71073 Å

Crystal system Orthorhombic

Space group Pca2(1)

Unit cell dimensions a = 18.3347(14) Å α= 90°

b = 12.3524(10) Å β= 90°

c = 19.2887(14) Å γ = 90°

Volume 4368.5(6) Å3

Z, Z’ 8, 2

Density (calculated) 1.478 g/cm3

Absorption coefficient 0.259 mm-1

F(000) 2016

Crystal size 0.25 x 0.20 x 0.08 mm3

Crystal color, habit Colorless block

Theta range for data collection 1.65 to 25.37°

Index ranges -22<=h<=21, -14<=k<=14, -19<=l<=23

Reflections collected 23569

Independent reflections 7697 [R(int) = 0.0631]

Completeness to theta = 25.00° 99.7 %

Absorption correction Multi-scan

Max. and min. transmission 0.9795 and 0.9380

Refinement method Full-matrix least-squares on F2

Data / restraints / parameters 7697 / 1 / 578

189

Goodness-of-fit on F2 1.003

Final R indices [I>2sigma(I)] R1 = 0.0794, wR2 = 0.1991

R indices (all data) R1 = 0.1214, wR2 = 0.2282

Absolute structure parameter 0.56(19)

Largest diff. peak and hole 0.950 and -0.561 e Å-3

Table C.7: Atomic coordinates (x 104) and equivalent isotropic displacement parameters

(Å2x 103)for Li[B(DPC)(Oxalato)]. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.

______

x y z U(eq)

______

P(1) 4867(1) 4704(2) 1490(1) 43(1)

P(1') -2238(1) 261(3) 1853(1) 64(1)

P(2') 468(1) 163(2) 3961(1) 37(1)

P(2) 2174(1) 4764(2) -634(1) 41(1)

O(1) 3166(2) 4351(4) 1797(2) 35(1)

O(1') -530(3) 679(6) 1565(3) 65(2)

O(2') 453(2) 620(5) 2322(2) 42(1)

O(2) 2187(3) 4368(5) 1024(2) 39(1)

O(3) 2152(2) 3124(4) 2012(2) 39(1)

O(3') 479(2) 1897(5) 1359(2) 45(2)

O(4) 1976(3) 4968(5) 2219(3) 45(1)

O(4') 638(3) 53(5) 1118(3) 42(1)

190

O(5) 1405(2) 2474(5) 2838(2) 41(1)

O(5') 1194(3) 2563(5) 515(2) 41(1)

O(6) 1149(3) 4830(6) 3058(3) 60(2)

O(6') 1440(3) 224(5) 233(2) 39(1)

O(7') -2862(3) -305(6) 2155(4) 63(2)

O(7) 5511(3) 5232(5) 1186(3) 54(2)

O(8) 4974(3) 3475(5) 1682(3) 63(2)

O(8') -2351(3) 1493(6) 1715(4) 82(3)

O(9) 4609(3) 5186(5) 2198(3) 52(2)

O(9') -2002(3) -195(8) 1126(3) 82(3)

O(10) 1464(3) 4758(5) -267(3) 51(2)

O(10') 1177(3) 341(5) 3635(3) 47(2)

O(11) 2290(3) 3853(5) -1197(3) 54(2)

O(11') 273(4) 961(4) 4559(3) 52(2)

O(12) 2339(4) 5744(5) -1110(4) 76(2)

O(12') 387(3) -950(4) 4336(3) 52(2)

C(1) 3408(4) 4523(6) 1130(4) 31(2)

C(1') -764(4) 448(9) 2216(4) 54(3)

C(2) 4113(4) 4691(6) 905(4) 36(2)

C(2') -1467(4) 226(8) 2414(4) 49(2)

C(3) 4209(4) 4827(7) 193(5) 41(2)

C(3') -1570(5) 47(7) 3151(4) 45(2)

C(4) 3632(5) 4804(7) -263(4) 44(2)

191

C(4') -1005(4) 32(6) 3590(4) 39(2)

C(5) 2910(4) 4697(6) -35(4) 31(2)

C(5') -269(4) 203(7) 3374(3) 34(2)

C(6) 2814(4) 4537(6) 677(4) 33(2)

C(6') -172(4) 400(7) 2671(4) 40(2)

C(7) 1696(4) 3224(7) 2527(4) 38(2)

C(7') 933(4) 1797(8) 830(4) 39(2)

C(8') 1042(4) 606(7) 670(3) 36(2)

C(8) 1573(4) 4422(8) 2642(4) 44(2)

C(9) 4466(7) 6334(8) 2274(6) 83(4)

C(9') -1657(15) -1432(14) 1085(8) 198(13)

C(10') -1906(8) -1744(16) 329(17) 213(15)

C(10) 4268(15) 6590(17) 2925(8) 209(12)

C(11) 5425(6) 3178(10) 2256(7) 87(4)

C(11') -2890(5) 1837(13) 1178(9) 132(7)

C(12') -2835(5) 2853(9) 1036(7) 80(4)

C(12) 5409(8) 1994(10) 2307(8) 108(5)

C(13') 893(5) -1254(7) 4865(5) 54(2)

C(13) 2377(8) 6786(10) -961(7) 93(4)

C(14) 2806(8) 7441(9) -1502(8) 108(5)

C(14') 828(6) -2392(9) 5013(7) 90(4)

C(15) 1912(5) 2854(8) -1171(5) 57(2)

C(15') 175(7) 2125(8) 4440(7) 86(4)

192

C(16') -430(6) 2476(10) 4882(7) 88(4)

C(16) 1210(7) 3059(17) -1598(8) 142(7)

B(1) 2381(5) 4231(8) 1761(4) 37(2)

B(1') 252(4) 811(10) 1596(5) 49(3)

Li(1) 6229(7) 5833(12) 596(6) 44(3)

Li(1') 1436(6) 882(14) 2737(7) 50(4)

______

Table C.8: Bond lengths [Å] and angles [°] for Li[B(DPC)(Oxalato)].

______

P(1)-O(7) 1.470(6) P(2)-O(12) 1.550(7)

P(1)-O(9) 1.565(6) P(2)-O(11) 1.578(7)

P(1)-O(8) 1.574(7) P(2)-C(5) 1.778(7)

P(1)-C(2) 1.784(8) P(2)-Li(1)#1 3.028(12)

P(1')-O(7') 1.462(6) O(1)-C(1) 1.377(8)

P(1')-O(8') 1.558(8) O(1)-B(1) 1.449(10)

P(1')-O(9') 1.572(9) O(1')-C(1') 1.358(8)

P(1')-C(2') 1.783(8) O(1')-B(1') 1.445(10)

P(2')-O(10') 1.460(6) O(2')-C(6') 1.357(8)

P(2')-O(11') 1.559(6) O(2')-B(1') 1.466(10)

P(2')-O(12') 1.561(6) O(2')-Li(1') 1.999(12)

P(2')-C(5') 1.763(8) O(2)-C(6) 1.347(9)

P(2')-Li(1') 3.084(15) O(2)-B(1) 1.473(9)

P(2)-O(10) 1.481(6) O(2)-Li(1)#1 1.957(14)

193

O(3)-C(7) 1.304(8) O(11')-C(15') 1.467(11)

O(3)-B(1) 1.511(11) O(12)-C(13) 1.321(13)

O(3')-C(7') 1.323(8) O(12')-C(13') 1.431(10)

O(3')-B(1') 1.477(13) C(1)-C(2) 1.379(10)

O(4)-C(8) 1.290(10) C(1)-C(6) 1.397(10)

O(4)-B(1) 1.472(11) C(1')-C(2') 1.372(10)

O(4')-C(8') 1.328(9) C(1')-C(6') 1.397(11)

O(4')-B(1') 1.493(11) C(2)-C(3) 1.394(11)

O(5)-C(7) 1.225(9) C(2')-C(3') 1.449(11)

O(5)-Li(1') 1.977(18) C(3)-C(4) 1.376(12)

O(5')-C(7') 1.221(9) C(3')-C(4') 1.339(12)

O(5')-Li(1)#1 1.989(17) C(4)-C(5) 1.402(11)

O(6)-C(8) 1.227(9) C(4')-C(5') 1.428(11)

O(6')-C(8') 1.211(8) C(5)-C(6) 1.398(10)

O(7')-Li(1')#2 1.850(14) C(5')-C(6') 1.390(10)

O(7)-Li(1) 1.892(14) C(7)-C(8) 1.513(12)

O(8)-C(11) 1.430(13) C(7')-C(8') 1.517(12)

O(8')-C(11') 1.493(11) C(9)-C(10) 1.345(16)

O(9)-C(9) 1.449(11) C(9')-C(10') 1.58(3)

O(9')-C(9') 1.66(2) C(11)-C(12) 1.467(16)

O(10)-Li(1)#1 1.867(13) C(11')-C(12') 1.289(15)

O(10')-Li(1') 1.916(16) C(13')-C(14') 1.440(13)

O(11)-C(15) 1.417(11) C(13)-C(14) 1.538(17)

194

C(15)-C(16) 1.548(16) Li(1)-O(5')#3 1.989(17)

C(15')-C(16') 1.465(15) Li(1)-P(2)#3 3.028(12)

Li(1)-O(10)#3 1.867(13) Li(1')-O(7')#4 1.850(14)

Li(1)-O(2)#3 1.957(14)

O(7)-P(1)-O(9) 114.9(3) O(11')-P(2')-Li(1') 121.1(4)

O(7)-P(1)-O(8) 115.0(4) O(12')-P(2')-Li(1') 131.6(4)

O(9)-P(1)-O(8) 101.5(4) C(5')-P(2')-Li(1') 86.7(3)

O(7)-P(1)-C(2) 112.0(4) O(10)-P(2)-O(12) 117.3(4)

O(9)-P(1)-C(2) 108.7(4) O(10)-P(2)-O(11) 116.3(4)

O(8)-P(1)-C(2) 103.7(3) O(12)-P(2)-O(11) 97.0(4)

O(7')-P(1')-O(8') 115.5(4) O(10)-P(2)-C(5) 110.9(3)

O(7')-P(1')-O(9') 113.6(5) O(12)-P(2)-C(5) 105.8(4)

O(8')-P(1')-O(9') 103.6(4) O(11)-P(2)-C(5) 108.2(3)

O(7')-P(1')-C(2') 111.5(4) O(10)-P(2)-Li(1)#1 28.6(3)

O(8')-P(1')-C(2') 103.5(4) O(12)-P(2)-Li(1)#1 140.1(4)

O(9')-P(1')-C(2') 108.3(4) O(11)-P(2)-Li(1)#1 116.3(4)

O(10')-P(2')-O(11') 115.3(4) C(5)-P(2)-Li(1)#1 85.1(3)

O(10')-P(2')-O(12') 114.7(4) C(1)-O(1)-B(1) 106.9(5)

O(11')-P(2')-O(12') 101.1(3) C(1')-O(1')-B(1') 107.4(6)

O(10')-P(2')-C(5') 113.7(3) C(6')-O(2')-B(1') 107.1(5)

O(11')-P(2')-C(5') 106.3(4) C(6')-O(2')-Li(1') 126.5(6)

O(12')-P(2')-C(5') 104.4(4) B(1')-O(2')-Li(1') 125.6(6)

O(10')-P(2')-Li(1') 27.7(3) C(6)-O(2)-B(1) 106.9(6)

195

C(6)-O(2)-Li(1)#1 125.1(5) O(1')-C(1')-C(2') 126.7(7)

B(1)-O(2)-Li(1)#1 127.5(6) O(1')-C(1')-C(6') 110.1(6)

C(7)-O(3)-B(1) 109.7(6) C(2')-C(1')-C(6') 123.1(7)

C(7')-O(3')-B(1') 109.4(7) C(1)-C(2)-C(3) 116.5(7)

C(8)-O(4)-B(1) 110.2(7) C(1)-C(2)-P(1) 121.9(6)

C(8')-O(4')-B(1') 110.1(7) C(3)-C(2)-P(1) 121.6(6)

C(7)-O(5)-Li(1') 133.7(6) C(1')-C(2')-C(3') 115.2(7)

C(7')-O(5')-Li(1)#1 138.2(6) C(1')-C(2')-P(1') 124.8(6)

P(1')-O(7')-Li(1')#2 166.0(7) C(3')-C(2')-P(1') 119.7(6)

P(1)-O(7)-Li(1) 166.4(6) C(4)-C(3)-C(2) 122.1(7)

C(11)-O(8)-P(1) 120.1(6) C(4')-C(3')-C(2') 121.4(7)

C(11')-O(8')-P(1') 118.9(8) C(3)-C(4)-C(5) 121.8(7)

C(9)-O(9)-P(1) 121.0(6) C(3')-C(4')-C(5') 123.0(7)

P(1')-O(9')-C(9') 118.6(6) C(6)-C(5)-C(4) 116.2(7)

P(2)-O(10)-Li(1)#1 129.1(5) C(6)-C(5)-P(2) 123.3(6)

P(2')-O(10')-Li(1') 131.5(5) C(4)-C(5)-P(2) 120.5(6)

C(15)-O(11)-P(2) 122.1(6) C(6')-C(5')-C(4') 115.5(7)

C(15')-O(11')-P(2') 122.2(6) C(6')-C(5')-P(2') 122.3(6)

C(13)-O(12)-P(2) 129.9(9) C(4')-C(5')-P(2') 122.2(5)

C(13')-O(12')-P(2') 120.0(5) O(2)-C(6)-C(1) 110.7(6)

O(1)-C(1)-C(2) 128.3(6) O(2)-C(6)-C(5) 128.1(6)

O(1)-C(1)-C(6) 109.6(6) C(1)-C(6)-C(5) 121.2(7)

C(2)-C(1)-C(6) 122.2(7) O(2')-C(6')-C(5') 128.8(7)

196

O(2')-C(6')-C(1') 109.6(6) O(1)-B(1)-O(2) 105.9(6)

C(5')-C(6')-C(1') 121.4(7) O(4)-B(1)-O(2) 112.7(7)

O(5)-C(7)-O(3) 125.4(8) O(1)-B(1)-O(3) 110.7(6)

O(5)-C(7)-C(8) 127.1(7) O(4)-B(1)-O(3) 103.1(6)

O(3)-C(7)-C(8) 107.4(7) O(2)-B(1)-O(3) 110.3(7)

O(5')-C(7')-O(3') 123.9(8) O(1')-B(1')-O(2') 105.7(6)

O(5')-C(7')-C(8') 126.7(7) O(1')-B(1')-O(3') 111.6(8)

O(3')-C(7')-C(8') 109.3(7) O(2')-B(1')-O(3') 111.8(8)

O(6')-C(8')-O(4') 126.1(8) O(1')-B(1')-O(4') 111.9(8)

O(6')-C(8')-C(7') 126.8(7) O(2')-B(1')-O(4') 111.7(7)

O(4')-C(8')-C(7') 107.0(6) O(3')-B(1')-O(4') 104.2(6)

O(6)-C(8)-O(4) 124.2(9) O(10)#3-Li(1)-O(7) 123.0(8)

O(6)-C(8)-C(7) 126.3(8) O(10)#3-Li(1)-O(2)#3 96.9(6)

O(4)-C(8)-C(7) 109.6(6) O(7)-Li(1)-O(2)#3 108.7(7)

C(10)-C(9)-O(9) 111.9(13) O(10)#3-Li(1)-O(5')#3 109.1(7)

C(10')-C(9')-O(9') 99.2(17) O(7)-Li(1)-O(5')#3 114.5(7)

O(8)-C(11)-C(12) 107.2(10) O(2)#3-Li(1)-O(5')#3 100.9(6)

C(12')-C(11')-O(8') 111.9(11) O(10)#3-Li(1)-P(2)#3 22.3(3)

O(12')-C(13')-C(14') 110.1(8) O(7)-Li(1)-P(2)#3 140.7(7)

O(12)-C(13)-C(14) 113.1(10) O(2)#3-Li(1)-P(2)#3 77.7(4)

O(11)-C(15)-C(16) 104.2(10) O(5')#3-Li(1)-P(2)#3 101.5(5)

C(16')-C(15')-O(11') 107.0(9) O(7')#4-Li(1')-O(10') 125.9(9)

O(1)-B(1)-O(4) 114.2(7) O(7')#4-Li(1')-O(5) 117.6(8)

197

O(10')-Li(1')-O(5) 104.5(7)

O(7')#4-Li(1')-O(2') 108.8(7)

O(10')-Li(1')-O(2') 94.7(6)

O(5)-Li(1')-O(2') 100.0(6)

O(7')#4-Li(1')-P(2') 138.9(8)

O(10')-Li(1')-P(2') 20.8(2)

O(5)-Li(1')-P(2') 101.2(5)

O(2')-Li(1')-P(2') 75.0(4)

198

______

Symmetry transformations used to generate equivalent atoms:

#1 x-1/2,-y+1,z #2 x-1/2,-y,z #3 x+1/2,-y+1,z

#4 x+1/2,-y,z

Table C.9: Anisotropic displacement parameters (Å2x 103) for Li[B(DPC)(Oxalato)].

The anisotropic displacement factor exponent takes the form: -2π2[ h2 a*2U11 + ... + 2 h

k a* b* U12]

______

U11 U22 U33 U23 U13 U12

______

P(1) 38(1) 61(2) 30(1) 0(1) 2(1) -18(1)

P(1') 16(1) 117(2) 60(2) 51(2) 3(1) -1(1)

P(2') 55(1) 40(1) 15(1) 1(1) -8(1) 14(1)

P(2) 45(1) 48(1) 29(1) 10(1) 1(1) 2(1)

O(1) 22(2) 61(3) 22(3) 3(2) 4(2) 0(2)

O(1') 23(3) 149(6) 23(3) 32(4) 3(2) -8(3)

O(2') 13(2) 98(4) 14(3) 3(3) 2(2) 9(2)

O(2) 36(3) 61(4) 18(3) 1(2) 2(2) 8(2)

O(3) 22(2) 68(4) 26(3) -4(3) 12(2) 0(2)

O(3') 26(3) 93(4) 15(3) 5(3) 5(2) 10(3)

O(4) 36(3) 64(4) 36(3) 2(3) 2(3) 17(3)

O(4') 30(3) 90(4) 6(2) -8(2) 5(2) -21(3)

199

O(5) 21(2) 78(4) 24(3) 8(3) 0(2) 4(2)

O(5') 29(3) 75(4) 19(2) 7(3) 4(2) 8(3)

O(6) 48(4) 110(5) 22(3) -14(3) 0(3) 42(3)

O(6') 27(3) 80(4) 10(3) -4(2) 2(2) -8(3)

O(7') 26(3) 109(5) 54(4) 44(4) 18(3) 1(3)

O(7) 36(3) 71(4) 56(4) -8(3) 5(3) -19(3)

O(8) 70(4) 72(4) 46(4) -6(3) -20(3) -4(3)

O(8') 31(3) 121(6) 93(5) 78(5) -4(3) -7(3)

O(9) 42(3) 84(4) 31(3) -10(3) 1(3) -27(3)

O(9') 19(3) 189(9) 38(4) 62(5) -3(3) -16(4)

O(10) 41(3) 85(4) 25(3) 16(3) -1(2) 17(3)

O(10') 34(3) 81(4) 25(3) -7(3) -6(2) 18(3)

O(11) 60(4) 72(4) 30(3) -6(3) -7(3) -9(3)

O(11') 87(4) 37(3) 30(3) 7(2) 16(3) 17(3)

O(12) 99(6) 46(4) 84(5) 27(4) 22(4) 6(4)

O(12') 78(4) 28(3) 49(3) 9(3) -36(3) 0(3)

C(1) 22(3) 47(4) 25(4) 0(3) -5(3) -7(3)

C(1') 30(4) 115(8) 17(4) 25(4) 18(3) 11(4)

C(2) 33(4) 42(4) 33(4) 2(3) 4(3) -5(3)

C(2') 21(4) 99(7) 28(4) 26(4) 7(3) 8(4)

C(3) 31(4) 52(5) 39(5) -5(4) 10(4) -10(4)

C(3') 39(4) 74(6) 21(4) 23(4) 19(4) 6(4)

C(4) 54(5) 53(5) 25(5) -9(4) 14(4) -19(4)

200

C(4') 50(5) 51(5) 16(4) 10(3) 15(4) 11(4)

C(5) 37(4) 35(4) 19(4) 4(3) 0(3) -3(3)

C(5') 33(4) 58(5) 10(4) 6(3) 9(3) 13(3)

C(6) 33(4) 44(5) 20(4) 3(3) -2(3) 4(3)

C(6') 21(4) 74(6) 25(4) 11(4) 7(3) 2(4)

C(7) 16(3) 82(6) 17(3) 6(4) 2(3) 10(4)

C(7') 17(3) 84(6) 16(4) 2(4) -7(3) 3(4)

C(8') 17(3) 76(6) 14(4) -9(4) 3(3) -8(3)

C(8) 27(4) 84(6) 21(4) 0(4) -7(3) 20(4)

C(9) 111(9) 52(6) 87(8) -10(5) 61(7) -10(6)

C(9') 410(30) 116(13) 68(9) -45(9) 99(15) -161(18)

C(10') 62(10) 145(16) 430(50) 70(20) 31(17) -18(10)

C(10) 390(30) 177(19) 61(10) -34(10) 102(15) -60(20)

C(11) 54(6) 92(9) 115(10) -44(8) -9(6) 19(6)

C(11') 34(5) 167(14) 195(15) 132(12) -60(7) -30(7)

C(12') 51(6) 72(7) 117(10) 43(7) -29(6) 3(5)

C(12) 110(11) 85(9) 129(12) -36(8) 19(9) -28(8)

C(13') 49(5) 56(5) 57(5) 18(4) 0(4) 6(4)

C(13) 101(9) 102(10) 77(8) -29(7) 0(7) 0(7)

C(14) 149(13) 50(7) 125(12) 36(7) 32(10) 7(7)

C(14') 69(7) 87(8) 115(10) 61(7) 27(7) 25(6)

C(15) 68(6) 62(6) 42(5) -12(4) 11(4) -2(5)

C(15') 119(10) 42(6) 96(9) 0(6) 30(8) 25(6)

201

C(16') 71(8) 92(8) 102(9) -16(7) 20(7) 38(6)

C(16) 61(8) 240(20) 123(12) -8(13) -23(8) -28(10)

B(1) 41(5) 58(6) 12(4) 5(4) -2(3) 4(4)

B(1') 15(4) 107(9) 27(5) 2(5) 10(3) 0(5)

Li(1) 39(7) 72(10) 20(6) -6(6) 11(5) -8(6)

Li(1') 13(6) 98(11) 37(8) -12(7) -9(5) 15(6)

Table C.10: Hydrogen coordinates (x 104) and isotropic displacement parameters (Å2 x

10 3) for Li[B(DPC)(Oxalato)].

______

x y z U(eq)

______

H(3A) 4687 4939 17 49

H(3'A) -2049 -62 3325 54

H(4A) 3726 4862 -746 53

H(4'A) -1098 -97 4067 47

H(9A) 4910 6746 2148 100

H(9B) 4072 6548 1951 100

H(9'A) -1120 -1430 1132 238

H(9'B) -1873 -1917 1438 238

H(10A) -1750 -2485 225 320

H(10B) -1685 -1244 -4 320

H(10C) -2439 -1698 297 320

202

H(10E) 4183 7372 2957 313

H(10F) 4658 6384 3247 313

H(10G) 3820 6202 3047 313

H(11A) 5237 3507 2689 105

H(11B) 5930 3434 2181 105

H(11C) -2812 1410 751 159

H(11D) -3390 1684 1347 159

H(12A) -3162 3032 651 120

H(12B) -2331 3018 903 120

H(12C) -2969 3280 1444 120

H(12D) 5724 1759 2688 162

H(12E) 5583 1678 1871 162

H(12F) 4908 1753 2395 162

H(13A) 795 -830 5291 65

H(13B) 1396 -1090 4710 65

H(13C) 2613 6875 -503 112

H(13D) 1876 7082 -928 112

H(14A) 2821 8204 -1363 162

H(14B) 2567 7379 -1955 162

H(14C) 3305 7159 -1535 162

H(14D) 1181 -2593 5373 136

H(14E) 926 -2809 4591 136

H(14F) 333 -2549 5177 136

203

H(15A) 1792 2655 -687 69

H(15B) 2207 2267 -1381 69

H(15C) 625 2523 4561 103

H(15D) 60 2264 3946 103

H(16A) -503 3258 4828 132

H(16B) -317 2313 5367 132

H(16C) -876 2094 4746 132

H(16D) 917 2396 -1611 213

H(16E) 1342 3270 -2071 213

H(16F) 927 3641 -1381 213

Table C.11: Crystal data and structure refinement for H2-DPN.

Compound Name H2-DPN

Empirical formula C18 H26 O8 P2

Formula weight 432.33

Temperature 100(2) K

Wavelength 0.71073 Å

204

Crystal system Monoclinic

Space group P2(1)/c

Unit cell dimensions a = 9.9232(4) Å α= 90°

b = 24.3489(9) Å β= 90.4330(1)°

c = 8.3888(3) Å γ = 90°

Volume 2026.84(1) Å3

Z 4

Density (calculated) 1.417 g/cm3

Absorption coefficient 0.257 mm-1

F(000) 912

Crystal size 0.35 x 0.30 x 0.23 mm3

Theta range for data collection 2.05 to 28.25°

Index ranges -12<=h<=13, -32<=k<=30, -5<=l<=11

Reflections collected 22805

Independent reflections 4992 [R(int) = 0.0354]

Completeness to theta = 25.00° 99.8 %

Absorption correction Multi-scan

Max. and min. transmission 0.9432 and 0.9154

Refinement method Full-matrix least-squares on F2

Data / restraints / parameters 4992 / 0 / 265

Goodness-of-fit on F2 1.046

Final R indices [I>2sigma(I)] R1 = 0.0400, wR2 = 0.0963

R indices (all data) R1 = 0.0530, wR2 = 0.1040

205

Largest diff. peak and hole 0.629 and -0.507 e Å-3

206

Table C.12: Atomic coordinates (x 104) and equivalent isotropic displacement

2 3 parameters (Å x 10 ) for H2-DPN. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.

______

x y z U(eq)

______

P(1) 642(1) 3845(1) 9186(1) 15(1)

P(2) -4083(1) 3265(1) 4154(1) 19(1)

O(5) -1642(1) 2582(1) 5199(2) 20(1)

O(2) 84(1) 3981(1) 10887(1) 19(1)

O(3) 1225(1) 4430(1) 8769(1) 19(1)

O(4) 222(1) 2816(1) 7160(2) 20(1)

O(7) -5508(1) 3356(1) 4904(2) 22(1)

O(1) 1636(1) 3392(1) 9125(2) 24(1)

O(6) -3821(1) 2702(1) 3547(1) 23(1)

O(8) -4104(2) 3726(1) 2850(2) 38(1)

C(1) -729(2) 3207(1) 7029(2) 13(1)

C(8) -2854(2) 3968(1) 6445(2) 12(1)

C(9) -2820(2) 3447(1) 5605(2) 13(1)

C(4) -1867(2) 4604(1) 8380(2) 14(1)

C(7) -3893(2) 4359(1) 6185(2) 17(1)

C(2) -735(2) 3703(1) 7845(2) 12(1)

C(10) -1791(2) 3077(1) 5903(2) 14(1)

207

C(3) -1816(2) 4093(1) 7569(2) 11(1)

C(5) -2880(2) 4977(1) 8087(2) 18(1)

C(6) -3905(2) 4853(1) 6980(2) 19(1)

C(11) -63(2) 3542(1) 12077(2) 24(1)

C(18) -4915(2) 3902(1) 206(2) 25(1)

C(15) -5865(2) 3057(1) 6365(2) 22(1)

C(16) -6606(2) 2535(1) 5962(2) 27(1)

C(17) -3835(2) 3626(1) 1173(2) 26(1)

C(13) 1813(2) 4523(1) 7204(2) 29(1)

C(12) 1059(2) 3578(1) 13266(2) 33(1)

C(14) 1562(6) 5065(2) 6696(6) 152(3)

______

208

Table C.13: Bond lengths [Å] and angles [°] for H2-DPN.

______

P(1)-O(1) 1.481(1) C(1)-C(10) 1.445(2)

P(1)-O(2) 1.569(1) C(8)-C(7) 1.420(2)

P(1)-O(3) 1.575(1) C(8)-C(3) 1.424(2)

P(1)-C(2) 1.797(2) C(8)-C(9) 1.451(2)

P(2)-O(6) 1.484(1) C(9)-C(10) 1.383(2)

P(2)-O(7) 1.567(1) C(4)-C(5) 1.376(2)

P(2)-O(8) 1.568(1) C(4)-C(3) 1.421(2)

P(2)-C(9) 1.796(2) C(7)-C(6) 1.374(2)

O(5)-C(10) 1.349(2) C(2)-C(3) 1.450(2)

O(2)-C(11) 1.471(2) C(5)-C(6) 1.406(2)

O(3)-C(13) 1.458(2) C(11)-C(12) 1.492(3)

O(4)-C(1) 1.345(2) C(18)-C(17) 1.499(2)

O(7)-C(15) 1.471(2) C(15)-C(16) 1.507(3)

O(8)-C(17) 1.454(2) C(13)-C(14) 1.409(4)

C(1)-C(2) 1.387(2)

209

O(1)-P(1)-O(2) 115.33(7)

O(1)-P(1)-O(3) 114.82(7)

O(2)-P(1)-O(3) 98.33(7)

O(1)-P(1)-C(2) 109.69(7)

O(2)-P(1)-C(2) 109.73(7)

O(3)-P(1)-C(2) 108.31(7)

O(6)-P(2)-O(7) 115.42(7)

O(6)-P(2)-O(8) 115.02(8)

O(7)-P(2)-O(8) 99.86(8)

O(6)-P(2)-C(9) 109.71(8)

O(7)-P(2)-C(9) 108.65(7)

O(8)-P(2)-C(9) 107.53(8)

C(11)-O(2)-P(1) 120.11(11)

C(13)-O(3)-P(1) 119.36(11)

C(15)-O(7)-P(2) 119.20(11)

C(17)-O(8)-P(2) 123.55(13)

O(4)-C(1)-C(2) 125.56(15)

O(4)-C(1)-C(10) 113.91(14)

C(2)-C(1)-C(10) 120.52(14)

C(7)-C(8)-C(3) 118.63(14)

C(7)-C(8)-C(9) 122.09(14)

C(3)-C(8)-C(9) 119.29(14)

C(10)-C(9)-C(8) 120.06(14)

210

C(10)-C(9)-P(2) 118.18(12)

C(8)-C(9)-P(2) 121.75(12)

C(5)-C(4)-C(3) 121.47(15)

C(6)-C(7)-C(8) 121.41(15)

C(1)-C(2)-C(3) 119.79(14)

C(1)-C(2)-P(1) 118.09(12)

C(3)-C(2)-P(1) 122.10(11)

O(5)-C(10)-C(9) 125.82(14)

O(5)-C(10)-C(1) 113.59(14)

C(9)-C(10)-C(1) 120.58(14)

C(4)-C(3)-C(8) 118.46(14)

C(4)-C(3)-C(2) 121.79(14)

C(8)-C(3)-C(2) 119.75(13)

C(4)-C(5)-C(6) 119.98(15)

C(7)-C(6)-C(5) 120.05(15)

O(2)-C(11)-C(12) 109.49(15)

O(7)-C(15)-C(16) 110.58(15)

O(8)-C(17)-C(18) 108.21(15)

C(14)-C(13)-O(3) 110.33(19)

______

2 3 Table C.14: Anisotropic displacement parameters (Å x 10 ) for H2-DPN. The anisotropic displacement factor exponent takes the form: -2π2[ h2 a*2U11 + ... + 2 h k a*

211

b* U12]

______

U11 U22 U33 U23

______

P(1) 14(1) 14(1) 16(1) -2(1)

P(2) 27(1) 17(1) 12(1) -1(1)

O(5) 24(1) 14(1) 22(1) -9(1)

O(2) 27(1) 17(1) 14(1) 2(1)

O(3) 18(1) 20(1) 19(1) -4(1)

O(4) 18(1) 15(1) 27(1) -5(1)

O(7) 21(1) 19(1) 26(1) 3(1)

O(1) 19(1) 23(1) 31(1) -6(1)

O(6) 29(1) 22(1) 19(1) -7(1)

O(8) 78(1) 24(1) 11(1) 2(1)

C(1) 13(1) 11(1) 15(1) 0(1)

C(8) 15(1) 12(1) 10(1) 1(1)

C(9) 17(1) 14(1) 9(1) -1(1)

C(4) 17(1) 12(1) 14(1) -1(1)

C(7) 20(1) 16(1) 14(1) 1(1)

C(2) 12(1) 12(1) 12(1) 0(1)

C(10) 18(1) 11(1) 12(1) -2(1)

C(3) 13(1) 11(1) 10(1) 1(1)

C(5) 23(1) 13(1) 19(1) -4(1)

212

C(6) 21(1) 16(1) 20(1) 2(1)

C(11) 25(1) 23(1) 23(1) 8(1)

C(18) 27(1) 28(1) 19(1) -1(1)

C(15) 18(1) 23(1) 25(1) -1(1)

C(16) 21(1) 24(1) 37(1) 0(1)

C(17) 20(1) 42(1) 16(1) 6(1)

C(13) 31(1) 31(1) 26(1) -3(1)

C(12) 38(1) 41(1) 19(1) 5(1)

C(14) 254(6) 59(2) 146(4) 66(2)

Table C.15: Hydrogen coordinates (x 104) and isotropic displacement parameters (Å2 x

3 10 ) for H2-DPN.

______

x y z U(eq)

______

H(4A) -1187 4691 9143 17

H(7A) -4595 4278 5445 20

H(5A) -2886 5319 8631 22

H(6A) -4608 5109 6782 23

H(11A) -44 3180 11543 28

H(11B) -939 3580 12623 28

H(18A) -4744 3843 -930 37

H(18B) -4912 4297 435 37

213

H(18C) -5794 3747 481 37

H(15A) -6440 3292 7041 26

H(15B) -5035 2968 6975 26

H(16A) -6840 2342 6948 41

H(16B) -6029 2299 5311 41

H(16C) -7431 2623 5366 41

H(17A) -3835 3226 957 31

H(17B) -2941 3775 889 31

H(13A) 2797 4457 7258 35

H(13B) 1419 4261 6426 35

H(12A) 927 3301 14099 49

H(12B) 1068 3945 13747 49

H(12C) 1919 3512 12733 49

H(14A) 1820 5103 5576 228

H(14B) 2092 5320 7350 228

H(14C) 601 5148 6808 228

H(1) 800(30) 2925(11) 7840(30) 49(8)

H(2) -2320(30) 2554(12) 4490(30) 56(8)

Table C.16: Crystal data and structure refinement for U.

214

Identification code U

Empirical formula C87 H112 B10 Li4 O48 P8

Formula weight 2309.39

Temperature 100(2) K

Wavelength 0.71073 Å

Crystal system Monoclinic

Space group P2(1)/c

Unit cell dimensions a = 36.109(2) Å α= 90°

b = 12.2057(7) Å β= 107.679(3)°

c = 25.5158(16) Å γ = 90°

Volume 10714.7(11) Å3

Z 4

Density (calculated) 1.432 g/cm3

Absorption coefficient 0.223 mm-1

F(000) 4800

215

Crystal size 0.40 x 0.40 x 0.10 mm3

Crystal color, habit Colorless plate

Theta range for data collection 2.07 to 25.48°

Index ranges -43<=h<=43, -14<=k<=14, -26<=l<=30

Reflections collected 98952

Independent reflections 19224 [R(int) = 0.1271]

Completeness to theta = 25.00° 98.3 %

Absorption correction Multi-scan

Max. and min. transmission 0.9780 and 0.9159

Refinement method Full-matrix least-squares on F2

Data / restraints / parameters 19224 / 0 / 1414

Goodness-of-fit on F2 1.032

Final R indices [I>2sigma(I)] R1 = 0.0805, wR2 = 0.1706

R indices (all data) R1 = 0.2027, wR2 = 0.2178

Largest diff. peak and hole 0.741 and -0.514 e Å-3

Table C.17: Atomic coordinates (x 104) and equivalent isotropic displacement parameters (Å2x 103) for U. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.

______

x y z U(eq)

______

P(1) 7680(1) 4012(1) 4214(1) 46(1)

216

P(2) 9315(1) 6055(1) 2902(1) 36(1)

P(3) 10474(1) 3975(1) 3943(1) 32(1)

P(4) 8538(1) 591(1) 4812(1) 33(1)

P(5) 4396(1) 6004(1) 885(1) 31(1)

P(6) 2668(1) 4066(1) -1161(1) 41(1)

P(7) 3481(1) 551(1) -490(1) 33(1)

P(8) 4495(1) 6017(1) -2109(1) 35(1)

O(1) 9569(1) 3149(3) 5460(1) 22(1)

O(2) 9577(1) 6937(3) 2740(2) 45(1)

O(3) 9129(1) 5407(4) 2363(2) 50(1)

O(4) 8698(1) 1610(3) 3327(2) 47(1)

O(5) 8819(1) 3119(3) 2838(2) 55(1)

O(6) 8517(1) 3398(3) 3537(1) 29(1)

O(7) 7255(1) 3678(4) 4180(2) 80(2)

O(8) 7802(1) 4729(3) 4748(2) 48(1)

O(9) 7931(1) 3065(3) 4229(2) 44(1)

O(10) 8323(1) 5055(3) 3880(1) 33(1)

O(11) 8596(1) 5096(3) 3112(1) 31(1)

O(12) 9541(1) 5385(3) 3370(1) 32(1)

O(13) 10860(1) 3389(3) 4273(2) 54(1)

O(14) 10256(1) 3105(3) 3506(2) 54(1)

O(15) 9030(1) 4150(3) 5604(1) 25(1)

O(16) 10237(1) 4381(3) 4284(1) 27(1)

217

O(17) 8990(1) 4683(3) 4015(1) 28(1)

O(18) 9554(1) 4120(3) 4649(1) 23(1)

O(19) 8512(1) 1289(3) 4327(1) 33(1)

O(20) 8935(1) -51(3) 5001(2) 37(1)

O(21) 8957(1) 3432(3) 4735(1) 26(1)

O(22) 9035(1) 2169(3) 5492(1) 27(1)

O(23) 8228(1) -342(3) 4707(2) 42(1)

O(24) 2229(1) 3767(4) -1300(2) 80(2)

O(25) 4021(1) 6535(3) 483(2) 41(1)

O(26) 4558(1) 6925(3) 1318(2) 43(1)

O(27) 4684(1) 5623(3) 619(1) 27(1)

O(28) 10153(1) 3671(3) 5295(1) 25(1)

O(29) 4507(1) 3105(3) 338(1) 24(1)

O(30) 5121(1) 3673(3) 298(1) 25(1)

O(31) 4563(1) 4114(3) -428(1) 23(1)

O(32) 4031(1) 3057(3) -2222(2) 49(1)

O(33) 3795(1) 1571(3) -1837(2) 44(1)

O(34) 3585(1) 3359(3) -1695(1) 30(1)

O(35) 4771(1) 6913(3) -2230(2) 40(1)

O(36) 4678(1) 5400(3) -1605(1) 39(1)

O(37) 2737(1) 4748(4) -634(2) 62(1)

O(38) 3934(1) 4101(3) 361(1) 26(1)

O(39) 3367(1) 5026(3) -1387(1) 29(1)

218

O(40) 3479(1) 1252(3) -965(2) 35(1)

O(41) 3880(1) -67(3) -254(2) 37(1)

O(42) 3176(1) -398(3) -625(2) 44(1)

O(43) 3949(1) 2117(3) 257(1) 27(1)

O(44) 3942(1) 3378(3) -474(1) 24(1)

O(45) 4040(1) 4627(3) -1149(1) 28(1)

O(46) 3716(1) 5071(3) -2081(1) 30(1)

O(47) 4405(1) 5212(3) -2610(2) 43(1)

O(48) 2924(1) 3109(3) -1096(2) 39(1)

C(1) 8028(3) 4371(8) 5250(4) 145(5)

C(2) 7082(2) 2807(8) 3947(5) 137(5)

C(3) 11093(2) 3155(7) 5219(4) 116(4)

C(4) 8122(2) 5180(7) 5670(3) 91(3)

C(5) 9905(2) 8207(5) 3492(3) 55(2)

C(6) 9948(2) 7279(5) 3124(3) 50(2)

C(7) 9237(2) 5211(6) 1502(3) 65(2)

C(8) 9357(2) 4844(6) 2083(2) 56(2)

C(9) 8886(2) 7907(5) 2920(2) 46(2)

C(10) 8567(2) 8478(5) 2953(2) 51(2)

C(11) 8263(2) 7919(5) 3041(2) 46(2)

C(12) 8266(2) 6798(5) 3103(2) 38(2)

C(13) 7926(2) 6224(5) 3184(2) 39(2)

C(14) 7548(2) 6555(5) 2875(2) 50(2)

219

C(15) 7224(2) 6090(6) 2964(3) 55(2)

C(16) 7269(2) 5328(6) 3365(3) 52(2)

C(17) 6660(2) 2700(7) 3871(4) 117(4)

C(18) 7634(2) 4945(5) 3676(2) 44(2)

C(19) 7962(2) 5388(5) 3570(2) 36(2)

C(20) 8596(2) 6213(5) 3079(2) 34(2)

C(21) 8906(2) 6761(5) 2978(2) 37(2)

C(22) 10914(2) 2711(8) 4712(3) 87(3)

C(23) 9812(2) 1914(5) 3771(3) 55(2)

C(24) 9855(2) 2777(5) 3400(2) 54(2)

C(25) 8130(2) 1023(5) 5571(2) 39(2)

C(26) 8085(2) 1544(5) 6020(3) 45(2)

C(27) 8354(2) 2305(5) 6300(2) 40(2)

C(28) 8681(2) 2581(5) 6135(2) 32(1)

C(29) 10569(2) 4863(5) 2993(2) 35(2)

C(30) 10720(2) 5621(5) 2714(2) 38(2)

C(31) 10953(2) 6466(5) 2995(2) 36(2)

C(32) 11039(1) 6579(4) 3562(2) 29(1)

C(33) 10877(1) 5825(4) 3840(2) 26(1)

C(34) 10643(1) 4964(4) 3557(2) 28(1)

C(35) 9385(2) -415(6) 4487(3) 71(2)

C(36) 9282(2) 342(5) 4882(3) 47(2)

C(37) 8719(2) 2034(4) 5667(2) 30(1)

220

C(38) 8452(2) 1255(5) 5387(2) 32(1)

C(39) 8149(2) -1022(5) 4227(2) 41(2)

C(40) 7850(2) -1859(5) 4266(3) 63(2)

C(41) 3013(2) 4611(8) -168(4) 128(5)

C(42) 2059(2) 3007(8) -1222(6) 190(7)

C(43) 1642(2) 2830(6) -1422(3) 74(2)

C(44) 5057(2) 8266(6) -1512(3) 85(3)

C(45) 2851(2) -2013(5) -1022(3) 69(2)

C(46) 3796(1) 3363(4) 1142(2) 30(1)

C(47) 3847(2) 3429(5) 1704(2) 36(2)

C(48) 4072(2) 4256(5) 2027(2) 42(2)

C(49) 4242(2) 5029(5) 1781(2) 40(2)

C(50) 3917(2) 6896(6) -465(3) 63(2)

C(51) 4043(2) 7352(5) 96(3) 55(2)

C(52) 5102(2) 8041(5) 1239(3) 58(2)

C(53) 4973(2) 7181(5) 1564(2) 49(2)

C(54) 4204(1) 4983(5) 1225(2) 28(1)

C(55) 3984(1) 4125(4) 907(2) 29(1)

C(56) 7243(3) 166(7) 3185(4) 80(3)

C(57) 5120(2) 7307(5) -1806(2) 50(2)

C(58) 4046(2) 7856(5) -2200(2) 44(2)

C(59) 3717(2) 8451(5) -2229(3) 51(2)

C(60) 3392(2) 7898(5) -2198(2) 46(2)

221

C(61) 2671(2) 6619(5) -2445(2) 41(2)

C(62) 2323(2) 6213(5) -2405(2) 43(2)

C(63) 2325(2) 5428(5) -2022(2) 37(2)

C(64) 3010(2) 5269(6) 293(3) 67(2)

C(65) 2673(2) 5011(4) -1685(2) 32(1)

C(66) 3026(2) 5403(5) -1739(2) 30(1)

C(67) 3027(2) 6235(5) -2114(2) 35(2)

C(68) 3389(2) 6769(5) -2133(2) 34(1)

C(69) 3527(1) 2543(4) 800(2) 30(1)

C(70) 3171(2) 2308(5) 890(2) 39(2)

C(71) 2916(2) 1544(5) 573(3) 42(2)

C(72) 3002(2) 995(5) 157(3) 40(2)

C(73) 4245(2) 346(5) -315(3) 51(2)

C(74) 4399(2) -370(7) -652(4) 97(3)

C(75) 3134(2) -1136(5) -1068(3) 45(2)

C(76) 3353(2) 1212(4) 49(2) 31(1)

C(77) 3608(2) 1984(4) 366(2) 29(1)

C(79) 3724(2) 6181(5) -2104(2) 31(1)

C(80) 4060(2) 6722(5) -2141(2) 35(2)

C(81) 4254(2) 5574(6) -3161(3) 59(2)

C(82) 3972(2) 4769(6) -3483(3) 87(3)

C(83) 7577(3) 731(7) 3155(5) 104(4)

C(84) 7718(2) 571(7) 2733(5) 78(3)

222

C(85) 7716(3) -294(10) 1901(4) 151(5)

C(86) 7073(2) -551(7) 2763(4) 80(3)

C(87) 7229(2) -692(6) 2343(4) 71(2)

C(88) 7540(3) -162(8) 2326(4) 86(3)

B(1) 9754(2) 3638(5) 5146(2) 21(1)

B(2) 8677(2) 2722(7) 3237(3) 41(2)

B(3) 9147(2) 4062(5) 4462(2) 24(2)

B(4) 9151(2) 3219(5) 5331(2) 24(2)

B(5) 8604(2) 4563(6) 3635(2) 28(2)

B(6) 4724(2) 3615(5) 77(2) 21(1)

B(7) 4085(2) 3169(5) 128(3) 27(2)

B(8) 4161(2) 4038(5) -687(2) 26(2)

B(9) 3802(2) 2695(6) -1922(3) 38(2)

B(10) 3673(2) 4528(6) -1582(3) 31(2)

Li(1) 9700(2) 5109(8) 4111(3) 30(2)

Li(2) 8442(2) 2848(8) 4239(4) 35(2)

Li(3) 3442(2) 2837(8) -1030(4) 33(2)

Li(4) 4787(2) 5097(7) -874(3) 27(2)

______

Table C.18: Bond lengths [Å] and angles [°] for U.

______

P(1)-O(9) 1.462(4)

223

P(1)-O(7) 1.565(5)

P(1)-O(8) 1.566(4)

P(1)-C(18) 1.752(7)

P(1)-Li(2) 3.081(9)

P(2)-O(12) 1.472(4)

P(2)-O(3) 1.553(4)

P(2)-O(2) 1.568(4)

P(2)-C(21) 1.772(6)

P(3)-O(16) 1.480(3)

P(3)-O(13) 1.564(4)

P(3)-O(14) 1.569(4)

P(3)-C(34) 1.778(5)

P(4)-O(19) 1.481(4)

P(4)-O(23) 1.562(4)

P(4)-O(20) 1.575(4)

P(4)-C(38) 1.787(6)

P(4)-Li(2) 3.088(9)

P(5)-O(27) 1.479(3)

P(5)-O(26) 1.561(4)

P(5)-O(25) 1.568(4)

P(5)-C(54) 1.775(5)

P(6)-O(48) 1.468(4)

P(6)-O(37) 1.535(5)

224

P(6)-O(24) 1.556(4)

P(6)-C(65) 1.771(6)

P(6)-Li(3) 3.100(9)

P(7)-O(40) 1.482(4)

P(7)-O(42) 1.563(4)

P(7)-O(41) 1.576(4)

P(7)-C(76) 1.773(6)

P(7)-Li(3) 3.096(9)

P(8)-O(36) 1.464(4)

P(8)-O(47) 1.567(4)

P(8)-O(35) 1.571(4)

P(8)-C(80) 1.772(6)

O(1)-B(1) 1.328(7)

O(1)-B(4) 1.448(6)

O(2)-C(6) 1.459(7)

O(3)-C(8) 1.421(7)

O(4)-B(2) 1.376(9)

O(5)-B(2) 1.360(8)

O(6)-B(2) 1.367(8)

O(6)-B(5) 1.462(7)

O(6)-Li(2) 2.007(10)

O(7)-C(2) 1.284(11)

O(8)-C(1) 1.364(8)

225

O(9)-Li(2) 1.857(9)

O(10)-C(19) 1.365(6)

O(10)-B(5) 1.471(7)

O(11)-C(20) 1.365(6)

O(11)-B(5) 1.478(7)

O(12)-Li(1) 1.833(9)

O(13)-C(22) 1.357(8)

O(14)-C(24) 1.447(7)

O(15)-C(33)#1 1.356(6)

O(15)-B(4) 1.467(7)

O(16)-Li(1) 2.055(9)

O(17)-B(3) 1.343(7)

O(17)-B(5) 1.445(6)

O(17)-Li(1) 2.552(9)

O(18)-B(1) 1.386(6)

O(18)-B(3) 1.401(6)

O(18)-Li(1) 2.014(9)

O(19)-Li(2) 1.923(10)

O(20)-C(36) 1.458(6)

O(21)-B(3) 1.356(7)

O(21)-B(4) 1.490(6)

O(21)-Li(2) 2.034(9)

O(22)-C(37) 1.357(6)

226

O(22)-B(4) 1.446(7)

O(23)-C(39) 1.434(6)

O(24)-C(42) 1.165(9)

O(25)-C(51) 1.423(7)

O(26)-C(53) 1.473(6)

O(27)-Li(4)#2 2.021(9)

O(28)-B(1) 1.377(6)

O(28)-Li(1)#1 2.074(10)

O(29)-B(6) 1.328(7)

O(29)-B(7) 1.455(6)

O(30)-B(6) 1.376(6)

O(30)-Li(4)#2 2.056(9)

O(31)-B(6) 1.383(6)

O(31)-B(8) 1.404(6)

O(31)-Li(4) 1.987(9)

O(32)-B(9) 1.361(8)

O(33)-B(9) 1.390(8)

O(34)-B(9) 1.370(8)

O(34)-B(10) 1.471(7)

O(34)-Li(3) 2.023(10)

O(35)-C(57) 1.471(6)

O(36)-Li(4) 1.824(9)

O(37)-C(41) 1.310(8)

227

O(38)-C(55) 1.348(6)

O(38)-B(7) 1.463(7)

O(39)-C(66) 1.366(6)

O(39)-B(10) 1.471(7)

O(40)-Li(3) 1.942(10)

O(41)-C(73) 1.462(6)

O(42)-C(75) 1.416(6)

O(43)-C(77) 1.351(6)

O(43)-B(7) 1.448(7)

O(44)-B(8) 1.353(7)

O(44)-B(7) 1.486(7)

O(44)-Li(3) 2.038(9)

O(45)-B(8) 1.335(7)

O(45)-B(10) 1.450(7)

O(45)-Li(4) 2.638(9)

O(46)-C(79) 1.357(6)

O(46)-B(10) 1.485(7)

O(47)-C(81) 1.415(7)

O(48)-Li(3) 1.855(9)

C(1)-C(4) 1.420(10)

C(2)-C(17) 1.481(9)

C(3)-C(22) 1.370(10)

C(5)-C(6) 1.508(8)

228

C(7)-C(8) 1.482(8)

C(9)-C(10) 1.370(8)

C(9)-C(21) 1.406(8)

C(10)-C(11) 1.367(8)

C(11)-C(12) 1.378(8)

C(12)-C(20) 1.405(7)

C(12)-C(13) 1.481(8)

C(13)-C(19) 1.396(8)

C(13)-C(14) 1.412(7)

C(14)-C(15) 1.379(9)

C(15)-C(16) 1.357(9)

C(16)-C(18) 1.396(8)

C(18)-C(19) 1.400(8)

C(20)-C(21) 1.394(8)

C(23)-C(24) 1.456(8)

C(25)-C(26) 1.362(8)

C(25)-C(38) 1.408(7)

C(26)-C(27) 1.376(8)

C(27)-C(28) 1.407(7)

C(28)-C(37) 1.412(7)

C(28)-C(32)#1 1.483(7)

C(29)-C(30) 1.374(7)

C(29)-C(34) 1.389(7)

229

C(30)-C(31) 1.386(7)

C(31)-C(32) 1.392(7)

C(32)-C(33) 1.394(7)

C(32)-C(28)#1 1.483(7)

C(33)-O(15)#1 1.356(6)

C(33)-C(34) 1.402(7)

C(35)-C(36) 1.494(8)

C(37)-C(38) 1.387(7)

C(39)-C(40) 1.511(8)

C(41)-C(64) 1.426(9)

C(42)-C(43) 1.452(9)

C(44)-C(57) 1.445(9)

C(45)-C(75) 1.509(8)

C(46)-C(55) 1.390(7)

C(46)-C(47) 1.392(7)

C(46)-C(69) 1.481(7)

C(47)-C(48) 1.397(8)

C(48)-C(49) 1.375(8)

C(49)-C(54) 1.385(7)

C(50)-C(51) 1.472(8)

C(52)-C(53) 1.495(8)

C(54)-C(55) 1.412(7)

C(56)-C(86) 1.378(11)

230

C(56)-C(83) 1.410(12)

C(58)-C(59) 1.376(8)

C(58)-C(80) 1.391(8)

C(59)-C(60) 1.377(8)

C(60)-C(68) 1.389(8)

C(61)-C(62) 1.382(8)

C(61)-C(67) 1.388(7)

C(62)-C(63) 1.367(8)

C(63)-C(65) 1.387(7)

C(65)-C(66) 1.407(7)

C(66)-C(67) 1.395(7)

C(67)-C(68) 1.472(7)

C(68)-C(79) 1.390(7)

C(69)-C(77) 1.403(7)

C(69)-C(70) 1.404(7)

C(70)-C(71) 1.388(8)

C(71)-C(72) 1.367(8)

C(72)-C(76) 1.403(7)

C(73)-C(74) 1.450(9)

C(76)-C(77) 1.393(7)

C(79)-C(80) 1.409(7)

C(81)-C(82) 1.474(8)

C(83)-C(84) 1.340(12)

231

C(84)-C(88) 1.373(12)

C(85)-C(88) 1.423(11)

C(86)-C(87) 1.365(11)

C(87)-C(88) 1.310(11)

B(1)-Li(1)#1 2.747(10)

B(3)-Li(1) 2.738(10)

B(5)-Li(2) 2.765(11)

B(6)-Li(4)#2 2.747(10)

B(8)-Li(4) 2.768(10)

B(10)-Li(3) 2.766(11)

Li(1)-O(28)#1 2.074(10)

Li(1)-B(1)#1 2.747(10)

Li(4)-O(27)#2 2.022(9)

Li(4)-O(30)#2 2.056(9)

Li(4)-B(6)#2 2.747(10)

232

O(9)-P(1)-O(7) 112.6(3)

O(9)-P(1)-O(8) 114.3(2)

O(7)-P(1)-O(8) 101.9(3)

O(9)-P(1)-C(18) 116.4(3)

O(7)-P(1)-C(18) 105.5(3)

O(8)-P(1)-C(18) 104.7(3)

O(9)-P(1)-Li(2) 24.8(2)

O(7)-P(1)-Li(2) 137.4(3)

O(8)-P(1)-Li(2) 103.1(2)

C(18)-P(1)-Li(2) 100.9(3)

O(12)-P(2)-O(3) 114.9(2)

O(12)-P(2)-O(2) 111.5(2)

O(3)-P(2)-O(2) 104.5(2)

O(12)-P(2)-C(21) 117.1(2)

O(3)-P(2)-C(21) 101.2(2)

O(2)-P(2)-C(21) 106.5(3)

O(16)-P(3)-O(13) 114.7(2)

O(16)-P(3)-O(14) 112.9(2)

O(13)-P(3)-O(14) 104.2(2)

O(16)-P(3)-C(34) 117.1(2)

O(13)-P(3)-C(34) 102.1(2)

O(14)-P(3)-C(34) 104.3(2)

O(19)-P(4)-O(23) 114.6(2)

233

O(19)-P(4)-O(20) 111.3(2)

O(23)-P(4)-O(20) 103.1(2)

O(19)-P(4)-C(38) 116.3(2)

O(23)-P(4)-C(38) 100.1(2)

O(20)-P(4)-C(38) 110.1(2)

O(19)-P(4)-Li(2) 28.6(2)

O(23)-P(4)-Li(2) 126.7(2)

O(20)-P(4)-Li(2) 123.4(2)

C(38)-P(4)-Li(2) 87.8(3)

O(27)-P(5)-O(26) 112.7(2)

O(27)-P(5)-O(25) 114.7(2)

O(26)-P(5)-O(25) 103.2(2)

O(27)-P(5)-C(54) 115.9(2)

O(26)-P(5)-C(54) 106.1(2)

O(25)-P(5)-C(54) 102.8(2)

O(48)-P(6)-O(37) 113.7(2)

O(48)-P(6)-O(24) 113.7(2)

O(37)-P(6)-O(24) 102.2(3)

O(48)-P(6)-C(65) 116.9(2)

O(37)-P(6)-C(65) 105.7(3)

O(24)-P(6)-C(65) 102.9(3)

O(48)-P(6)-Li(3) 23.9(2)

O(37)-P(6)-Li(3) 105.3(2)

234

O(24)-P(6)-Li(3) 137.1(3)

C(65)-P(6)-Li(3) 100.4(2)

O(40)-P(7)-O(42) 114.8(2)

O(40)-P(7)-O(41) 111.5(2)

O(42)-P(7)-O(41) 103.4(2)

O(40)-P(7)-C(76) 115.7(2)

O(42)-P(7)-C(76) 100.1(2)

O(41)-P(7)-C(76) 110.3(2)

O(40)-P(7)-Li(3) 29.2(2)

O(42)-P(7)-Li(3) 129.4(2)

O(41)-P(7)-Li(3) 121.0(2)

C(76)-P(7)-Li(3) 87.0(2)

O(36)-P(8)-O(47) 108.7(2)

O(36)-P(8)-O(35) 112.7(2)

O(47)-P(8)-O(35) 105.3(2)

O(36)-P(8)-C(80) 116.7(2)

O(47)-P(8)-C(80) 107.8(2)

O(35)-P(8)-C(80) 105.0(2)

B(1)-O(1)-B(4) 121.2(4)

C(6)-O(2)-P(2) 121.5(4)

C(8)-O(3)-P(2) 122.1(4)

B(2)-O(6)-B(5) 125.3(5)

B(2)-O(6)-Li(2) 119.5(5)

235

B(5)-O(6)-Li(2) 104.6(4)

C(2)-O(7)-P(1) 124.9(6)

C(1)-O(8)-P(1) 124.6(5)

P(1)-O(9)-Li(2) 135.9(4)

C(19)-O(10)-B(5) 122.4(4)

C(20)-O(11)-B(5) 119.6(4)

P(2)-O(12)-Li(1) 149.5(4)

C(22)-O(13)-P(3) 127.3(4)

C(24)-O(14)-P(3) 125.3(4)

C(33)#1-O(15)-B(4) 120.0(4)

P(3)-O(16)-Li(1) 134.1(3)

B(3)-O(17)-B(5) 125.8(4)

B(3)-O(17)-Li(1) 83.1(3)

B(5)-O(17)-Li(1) 145.3(4)

B(1)-O(18)-B(3) 119.5(4)

B(1)-O(18)-Li(1) 134.9(4)

B(3)-O(18)-Li(1) 105.2(4)

P(4)-O(19)-Li(2) 129.8(4)

C(36)-O(20)-P(4) 122.2(4)

B(3)-O(21)-B(4) 118.1(4)

B(3)-O(21)-Li(2) 112.8(4)

B(4)-O(21)-Li(2) 129.1(4)

C(37)-O(22)-B(4) 123.1(4)

236

C(39)-O(23)-P(4) 121.0(3)

C(42)-O(24)-P(6) 134.6(5)

C(51)-O(25)-P(5) 121.7(4)

C(53)-O(26)-P(5) 124.6(4)

P(5)-O(27)-Li(4)#2 135.8(3)

B(1)-O(28)-Li(1)#1 103.7(4)

B(6)-O(29)-B(7) 120.0(4)

B(6)-O(30)-Li(4)#2 104.6(4)

B(6)-O(31)-B(8) 119.4(4)

B(6)-O(31)-Li(4) 132.1(4)

B(8)-O(31)-Li(4) 108.2(4)

B(9)-O(34)-B(10) 122.7(5)

B(9)-O(34)-Li(3) 119.5(5)

B(10)-O(34)-Li(3) 103.6(4)

C(57)-O(35)-P(8) 122.5(4)

P(8)-O(36)-Li(4) 154.5(4)

C(41)-O(37)-P(6) 127.2(5)

C(55)-O(38)-B(7) 119.2(4)

C(66)-O(39)-B(10) 122.4(4)

P(7)-O(40)-Li(3) 128.9(4)

C(73)-O(41)-P(7) 122.9(4)

C(75)-O(42)-P(7) 123.0(4)

C(77)-O(43)-B(7) 123.1(4)

237

B(8)-O(44)-B(7) 117.1(4)

B(8)-O(44)-Li(3) 114.6(4)

B(7)-O(44)-Li(3) 128.2(4)

B(8)-O(45)-B(10) 127.3(4)

B(8)-O(45)-Li(4) 81.2(3)

B(10)-O(45)-Li(4) 147.8(4)

C(79)-O(46)-B(10) 119.5(4)

C(81)-O(47)-P(8) 122.5(4)

P(6)-O(48)-Li(3) 137.4(4)

O(8)-C(1)-C(4) 115.0(7)

O(7)-C(2)-C(17) 118.0(9)

O(2)-C(6)-C(5) 112.6(5)

O(3)-C(8)-C(7) 108.5(5)

C(10)-C(9)-C(21) 121.1(6)

C(11)-C(10)-C(9) 119.2(6)

C(10)-C(11)-C(12) 122.4(6)

C(11)-C(12)-C(20) 118.5(6)

C(11)-C(12)-C(13) 120.5(5)

C(20)-C(12)-C(13) 121.0(6)

C(19)-C(13)-C(14) 118.0(6)

C(19)-C(13)-C(12) 122.8(5)

C(14)-C(13)-C(12) 119.2(6)

C(15)-C(14)-C(13) 121.0(6)

238

C(16)-C(15)-C(14) 119.6(6)

C(15)-C(16)-C(18) 122.2(6)

C(16)-C(18)-C(19) 118.0(6)

C(16)-C(18)-P(1) 120.8(5)

C(19)-C(18)-P(1) 121.1(4)

O(10)-C(19)-C(13) 119.6(5)

O(10)-C(19)-C(18) 119.2(5)

C(13)-C(19)-C(18) 121.0(5)

O(11)-C(20)-C(21) 120.3(5)

O(11)-C(20)-C(12) 119.3(5)

C(21)-C(20)-C(12) 120.2(6)

C(20)-C(21)-C(9) 118.6(5)

C(20)-C(21)-P(2) 122.1(5)

C(9)-C(21)-P(2) 119.4(5)

O(13)-C(22)-C(3) 116.6(9)

O(14)-C(24)-C(23) 112.2(5)

C(26)-C(25)-C(38) 120.3(5)

C(25)-C(26)-C(27) 120.5(5)

C(26)-C(27)-C(28) 122.0(5)

C(27)-C(28)-C(37) 116.4(5)

C(27)-C(28)-C(32)#1 120.8(5)

C(37)-C(28)-C(32)#1 122.8(5)

C(30)-C(29)-C(34) 119.7(5)

239

C(29)-C(30)-C(31) 120.6(5)

C(30)-C(31)-C(32) 121.2(5)

C(31)-C(32)-C(33) 117.9(5)

C(31)-C(32)-C(28)#1 120.7(5)

C(33)-C(32)-C(28)#1 121.2(5)

O(15)#1-C(33)-C(32) 120.5(5)

O(15)#1-C(33)-C(34) 118.3(5)

C(32)-C(33)-C(34) 120.9(5)

C(29)-C(34)-C(33) 119.7(5)

C(29)-C(34)-P(3) 121.6(4)

C(33)-C(34)-P(3) 118.6(4)

O(20)-C(36)-C(35) 110.1(5)

O(22)-C(37)-C(38) 115.9(5)

O(22)-C(37)-C(28) 121.9(5)

C(38)-C(37)-C(28) 121.9(5)

C(37)-C(38)-C(25) 118.9(5)

C(37)-C(38)-P(4) 117.8(4)

C(25)-C(38)-P(4) 123.4(4)

O(23)-C(39)-C(40) 107.3(5)

O(37)-C(41)-C(64) 118.9(7)

O(24)-C(42)-C(43) 127.2(8)

C(55)-C(46)-C(47) 118.6(5)

C(55)-C(46)-C(69) 121.0(5)

240

C(47)-C(46)-C(69) 120.3(5)

C(46)-C(47)-C(48) 121.3(5)

C(49)-C(48)-C(47) 119.2(5)

C(48)-C(49)-C(54) 121.3(6)

O(25)-C(51)-C(50) 110.1(6)

O(26)-C(53)-C(52) 111.2(5)

C(49)-C(54)-C(55) 118.9(5)

C(49)-C(54)-P(5) 122.7(4)

C(55)-C(54)-P(5) 118.3(4)

O(38)-C(55)-C(46) 120.2(5)

O(38)-C(55)-C(54) 119.0(5)

C(46)-C(55)-C(54) 120.7(5)

C(86)-C(56)-C(83) 116.9(9)

C(44)-C(57)-O(35) 114.2(5)

C(59)-C(58)-C(80) 122.1(6)

C(58)-C(59)-C(60) 118.5(6)

C(59)-C(60)-C(68) 122.1(6)

C(62)-C(61)-C(67) 121.9(6)

C(63)-C(62)-C(61) 119.9(5)

C(62)-C(63)-C(65) 120.4(5)

C(63)-C(65)-C(66) 119.5(5)

C(63)-C(65)-P(6) 119.4(4)

C(66)-C(65)-P(6) 120.9(4)

241

O(39)-C(66)-C(67) 120.4(5)

O(39)-C(66)-C(65) 118.9(5)

C(67)-C(66)-C(65) 120.4(5)

C(61)-C(67)-C(66) 117.9(5)

C(61)-C(67)-C(68) 119.8(5)

C(66)-C(67)-C(68) 122.1(5)

C(60)-C(68)-C(79) 118.7(5)

C(60)-C(68)-C(67) 118.9(5)

C(79)-C(68)-C(67) 122.4(5)

C(77)-C(69)-C(70) 116.8(5)

C(77)-C(69)-C(46) 122.5(5)

C(70)-C(69)-C(46) 120.6(5)

C(71)-C(70)-C(69) 121.4(6)

C(72)-C(71)-C(70) 121.0(5)

C(71)-C(72)-C(76) 119.5(5)

C(74)-C(73)-O(41) 112.0(6)

O(42)-C(75)-C(45) 107.5(5)

C(77)-C(76)-C(72) 119.4(5)

C(77)-C(76)-P(7) 118.4(4)

C(72)-C(76)-P(7) 122.1(4)

O(43)-C(77)-C(76) 116.4(5)

O(43)-C(77)-C(69) 121.7(5)

C(76)-C(77)-C(69) 121.8(5)

242

O(46)-C(79)-C(68) 119.2(5)

O(46)-C(79)-C(80) 120.1(5)

C(68)-C(79)-C(80) 120.5(5)

C(58)-C(80)-C(79) 118.1(5)

C(58)-C(80)-P(8) 119.3(4)

C(79)-C(80)-P(8) 122.6(4)

O(47)-C(81)-C(82) 109.8(6)

C(84)-C(83)-C(56) 120.9(9)

C(83)-C(84)-C(88) 119.9(10)

C(87)-C(86)-C(56) 120.2(9)

C(88)-C(87)-C(86) 121.7(9)

C(87)-C(88)-C(84) 120.4(10)

C(87)-C(88)-C(85) 123.8(12)

C(84)-C(88)-C(85) 115.8(12)

O(1)-B(1)-O(28) 121.6(5)

O(1)-B(1)-O(18) 121.6(4)

O(28)-B(1)-O(18) 116.8(5)

O(1)-B(1)-Li(1)#1 102.8(4)

O(28)-B(1)-Li(1)#1 47.2(3)

O(18)-B(1)-Li(1)#1 117.4(4)

O(5)-B(2)-O(6) 121.6(7)

O(5)-B(2)-O(4) 117.6(6)

O(6)-B(2)-O(4) 120.9(6)

243

O(17)-B(3)-O(21) 127.4(5)

O(17)-B(3)-O(18) 112.9(5)

O(21)-B(3)-O(18) 119.6(5)

O(17)-B(3)-Li(1) 67.7(3)

O(21)-B(3)-Li(1) 164.8(4)

O(18)-B(3)-Li(1) 45.2(3)

O(22)-B(4)-O(1) 104.8(4)

O(22)-B(4)-O(15) 113.5(4)

O(1)-B(4)-O(15) 112.1(4)

O(22)-B(4)-O(21) 111.0(4)

O(1)-B(4)-O(21) 112.0(4)

O(15)-B(4)-O(21) 103.6(4)

O(17)-B(5)-O(6) 109.1(4)

O(17)-B(5)-O(10) 108.9(4)

O(6)-B(5)-O(10) 109.3(4)

O(17)-B(5)-O(11) 108.1(4)

O(6)-B(5)-O(11) 109.2(4)

O(10)-B(5)-O(11) 112.2(5)

O(17)-B(5)-Li(2) 91.5(4)

O(6)-B(5)-Li(2) 44.6(3)

O(10)-B(5)-Li(2) 77.5(3)

O(11)-B(5)-Li(2) 152.6(4)

O(29)-B(6)-O(30) 121.4(5)

244

O(29)-B(6)-O(31) 122.0(4)

O(30)-B(6)-O(31) 116.6(5)

O(29)-B(6)-Li(4)#2 104.0(4)

O(30)-B(6)-Li(4)#2 46.4(3)

O(31)-B(6)-Li(4)#2 115.5(4)

O(43)-B(7)-O(29) 104.9(4)

O(43)-B(7)-O(38) 113.8(4)

O(29)-B(7)-O(38) 111.6(4)

O(43)-B(7)-O(44) 110.6(4)

O(29)-B(7)-O(44) 112.7(4)

O(38)-B(7)-O(44) 103.4(4)

O(45)-B(8)-O(44) 126.9(5)

O(45)-B(8)-O(31) 113.3(5)

O(44)-B(8)-O(31) 119.8(5)

O(45)-B(8)-Li(4) 70.3(3)

O(44)-B(8)-Li(4) 162.6(4)

O(31)-B(8)-Li(4) 43.0(3)

O(32)-B(9)-O(34) 124.6(6)

O(32)-B(9)-O(33) 116.8(6)

O(34)-B(9)-O(33) 118.6(6)

O(45)-B(10)-O(39) 108.3(5)

O(45)-B(10)-O(34) 108.8(5)

O(39)-B(10)-O(34) 109.2(5)

245

O(45)-B(10)-O(46) 107.8(4)

O(39)-B(10)-O(46) 112.9(5)

O(34)-B(10)-O(46) 109.6(5)

O(45)-B(10)-Li(3) 91.3(4)

O(39)-B(10)-Li(3) 76.3(3)

O(34)-B(10)-Li(3) 45.3(3)

O(46)-B(10)-Li(3) 153.6(4)

O(12)-Li(1)-O(18) 138.4(5)

O(12)-Li(1)-O(16) 106.3(4)

O(18)-Li(1)-O(16) 91.1(4)

O(12)-Li(1)-O(28)#1 123.5(5)

O(18)-Li(1)-O(28)#1 89.7(4)

O(16)-Li(1)-O(28)#1 98.0(4)

O(12)-Li(1)-O(17) 87.0(3)

O(18)-Li(1)-O(17) 58.7(2)

O(16)-Li(1)-O(17) 141.8(4)

O(28)#1-Li(1)-O(17) 104.1(4)

O(12)-Li(1)-B(3) 113.0(4)

O(18)-Li(1)-B(3) 29.59(19)

O(16)-Li(1)-B(3) 117.5(4)

O(28)#1-Li(1)-B(3) 98.4(3)

O(17)-Li(1)-B(3) 29.14(16)

O(12)-Li(1)-B(1)#1 122.9(4)

246

O(18)-Li(1)-B(1)#1 98.4(3)

O(16)-Li(1)-B(1)#1 70.1(3)

O(28)#1-Li(1)-B(1)#1 29.15(18)

O(17)-Li(1)-B(1)#1 132.1(4)

B(3)-Li(1)-B(1)#1 118.5(3)

O(9)-Li(2)-O(19) 103.7(5)

O(9)-Li(2)-O(6) 110.0(5)

O(19)-Li(2)-O(6) 112.8(5)

O(9)-Li(2)-O(21) 132.5(5)

O(19)-Li(2)-O(21) 102.2(4)

O(6)-Li(2)-O(21) 95.4(4)

O(9)-Li(2)-B(5) 105.1(4)

O(19)-Li(2)-B(5) 140.5(5)

O(6)-Li(2)-B(5) 30.8(2)

O(21)-Li(2)-B(5) 77.0(3)

O(9)-Li(2)-P(1) 19.29(18)

O(19)-Li(2)-P(1) 122.9(4)

O(6)-Li(2)-P(1) 100.8(3)

O(21)-Li(2)-P(1) 119.5(4)

B(5)-Li(2)-P(1) 88.7(3)

O(9)-Li(2)-P(4) 95.9(4)

O(19)-Li(2)-P(4) 21.63(17)

O(6)-Li(2)-P(4) 134.0(4)

247

O(21)-Li(2)-P(4) 93.9(3)

B(5)-Li(2)-P(4) 158.0(4)

P(1)-Li(2)-P(4) 113.1(3)

O(48)-Li(3)-O(40) 103.2(5)

O(48)-Li(3)-O(34) 112.0(4)

O(40)-Li(3)-O(34) 110.9(5)

O(48)-Li(3)-O(44) 131.4(5)

O(40)-Li(3)-O(44) 103.9(4)

O(34)-Li(3)-O(44) 94.8(4)

O(48)-Li(3)-B(10) 105.7(4)

O(40)-Li(3)-B(10) 139.7(5)

O(34)-Li(3)-B(10) 31.1(2)

O(44)-Li(3)-B(10) 76.8(3)

O(48)-Li(3)-P(7) 96.4(4)

O(40)-Li(3)-P(7) 21.89(17)

O(34)-Li(3)-P(7) 132.0(4)

O(44)-Li(3)-P(7) 94.1(3)

B(10)-Li(3)-P(7) 156.8(4)

O(48)-Li(3)-P(6) 18.70(18)

O(40)-Li(3)-P(6) 121.9(4)

O(34)-Li(3)-P(6) 102.1(3)

O(44)-Li(3)-P(6) 119.9(4)

B(10)-Li(3)-P(6) 89.1(3)

248

P(7)-Li(3)-P(6) 113.7(3)

O(36)-Li(4)-O(31) 135.2(5)

O(36)-Li(4)-O(27)#2 107.8(4)

O(31)-Li(4)-O(27)#2 93.6(4)

O(36)-Li(4)-O(30)#2 121.4(5)

O(31)-Li(4)-O(30)#2 92.1(4)

O(27)#2-Li(4)-O(30)#2 99.0(4)

O(36)-Li(4)-O(45) 83.4(3)

O(31)-Li(4)-O(45) 57.3(2)

O(27)#2-Li(4)-O(45) 141.4(4)

O(30)#2-Li(4)-O(45) 106.2(3)

O(36)-Li(4)-B(6)#2 122.1(4)

O(31)-Li(4)-B(6)#2 101.8(3)

O(27)#2-Li(4)-B(6)#2 71.2(3)

O(30)#2-Li(4)-B(6)#2 28.99(18)

O(45)-Li(4)-B(6)#2 134.2(4)

O(36)-Li(4)-B(8) 109.7(4)

O(31)-Li(4)-B(8) 28.79(19)

O(27)#2-Li(4)-B(8) 118.9(4)

O(30)#2-Li(4)-B(8) 100.4(3)

O(45)-Li(4)-B(8) 28.46(16)

B(6)#2-Li(4)-B(8) 121.0(3)

249

______

Symmetry transformations used to generate equivalent atoms:

#1 -x+2,-y+1,-z+1 #2 -x+1,-y+1,-z

Table C.19: Anisotropic displacement parameters (Å2x 103) for U. The anisotropic

displacement factor exponent takes the form: -2π2[ h2 a*2U11 + ... + 2 h k a* b* U12]

______

U11 U22 U33 U23 U13

______

P(1) 26(1) 47(1) 68(1) -10(1)

P(2) 45(1) 39(1) 22(1) 6(1)

P(3) 44(1) 26(1) 30(1) 0(1)

P(4) 30(1) 32(1) 40(1) -2(1)

P(5) 33(1) 27(1) 37(1) -2(1)

P(6) 33(1) 41(1) 54(1) 8(1)

P(7) 29(1) 26(1) 46(1) 1(1)

P(8) 38(1) 43(1) 24(1) 6(1)

O(1) 19(2) 27(2) 21(2) 7(2)

O(2) 57(3) 45(3) 36(2) 13(2)

O(3) 54(3) 68(3) 27(2) -8(2)

O(4) 50(3) 36(3) 55(3) -16(2)

O(5) 74(3) 56(3) 45(3) -7(2)

O(6) 25(2) 34(2) 25(2) -4(2)

O(7) 24(2) 63(4) 153(5) -34(3)

250

O(8) 50(3) 48(3) 49(3) -2(2)

O(9) 26(2) 38(3) 71(3) -11(2)

O(10) 23(2) 45(3) 27(2) -4(2)

O(11) 33(2) 32(3) 22(2) -1(2)

O(12) 35(2) 39(2) 21(2) 9(2)

O(13) 77(3) 43(3) 50(3) 23(2)

O(14) 81(3) 43(3) 51(3) -20(2)

O(15) 25(2) 27(2) 23(2) 3(2)

O(16) 30(2) 30(2) 23(2) 0(2)

O(17) 23(2) 35(2) 23(2) 4(2)

O(18) 16(2) 32(2) 20(2) 5(2)

O(19) 28(2) 40(2) 29(2) -6(2)

O(20) 34(2) 35(2) 45(3) 1(2)

O(21) 18(2) 35(2) 25(2) -1(2)

O(22) 26(2) 30(2) 31(2) 3(2)

O(23) 44(2) 39(3) 49(3) -14(2)

O(24) 28(2) 53(3) 166(5) 37(3)

O(25) 32(2) 31(2) 59(3) 13(2)

O(26) 49(2) 39(3) 50(3) -15(2)

O(27) 24(2) 36(2) 26(2) 4(2)

O(28) 17(2) 30(2) 25(2) 2(2)

O(29) 18(2) 29(2) 24(2) 8(2)

O(30) 17(2) 33(2) 22(2) 3(2)

251

O(31) 17(2) 32(2) 17(2) 4(2)

O(32) 69(3) 51(3) 38(3) -5(2)

O(33) 50(2) 34(3) 45(3) -10(2)

O(34) 29(2) 31(2) 26(2) 2(2)

O(35) 35(2) 48(3) 34(2) 6(2)

O(36) 39(2) 52(3) 28(2) 17(2)

O(37) 73(3) 74(4) 41(3) 21(3)

O(38) 24(2) 32(2) 25(2) 4(2)

O(39) 21(2) 33(2) 28(2) 9(2)

O(40) 36(2) 27(2) 43(2) 5(2)

O(41) 33(2) 28(2) 53(3) 6(2)

O(42) 40(2) 37(3) 59(3) -9(2)

O(43) 20(2) 28(2) 35(2) 8(2)

O(44) 18(2) 31(2) 22(2) 5(2)

O(45) 24(2) 35(2) 21(2) 7(2)

O(46) 30(2) 31(2) 24(2) 7(2)

O(47) 48(2) 52(3) 23(2) 7(2)

O(48) 28(2) 31(2) 59(3) 9(2)

C(1) 129(8) 124(9) 105(8) -60(7)

C(2) 40(5) 95(8) 265(14) 63(9)

C(3) 96(7) 99(8) 121(8) -56(7)

C(4) 95(6) 89(7) 79(6) -22(5)

C(5) 55(4) 50(5) 52(4) 10(4)

252

C(6) 47(4) 40(4) 69(5) 9(4)

C(7) 79(5) 85(6) 36(4) -1(4)

C(8) 67(4) 64(5) 38(4) -5(4)

C(9) 52(4) 49(5) 33(4) 7(3)

C(10) 59(4) 38(4) 47(4) 12(3)

C(11) 54(4) 48(5) 30(4) -4(3)

C(12) 47(4) 39(4) 20(3) -1(3)

C(13) 26(3) 52(4) 29(4) -12(3)

C(14) 53(4) 49(4) 34(4) -7(3)

C(15) 21(3) 71(5) 58(5) -22(4)

C(16) 39(4) 52(5) 57(5) -20(4)

C(17) 28(4) 90(7) 223(11) 34(7)

C(18) 18(3) 63(5) 45(4) -23(3)

C(19) 30(3) 42(4) 26(3) -7(3)

C(20) 45(4) 41(4) 10(3) 3(3)

C(21) 49(4) 38(4) 20(3) 9(3)

C(22) 53(5) 142(9) 68(6) 16(6)

C(23) 55(4) 55(5) 55(5) -6(4)

C(24) 67(5) 45(4) 35(4) -5(3)

C(25) 34(3) 34(4) 54(4) -2(3)

C(26) 49(4) 46(4) 54(4) -6(4)

C(27) 50(4) 40(4) 44(4) -2(3)

C(28) 38(3) 34(4) 28(3) 6(3)

253

C(29) 44(4) 34(4) 30(4) -3(3)

C(30) 55(4) 42(4) 21(3) -1(3)

C(31) 45(4) 39(4) 30(4) 7(3)

C(32) 32(3) 26(3) 32(4) 0(3)

C(33) 25(3) 32(4) 24(3) 5(3)

C(34) 32(3) 27(3) 29(4) 3(3)

C(35) 82(5) 65(5) 83(6) -7(4)

C(36) 28(3) 59(5) 58(4) -2(4)

C(37) 32(3) 27(4) 32(4) 5(3)

C(38) 31(3) 33(4) 35(4) 1(3)

C(39) 41(3) 45(4) 39(4) -11(3)

C(40) 68(5) 55(5) 79(5) -28(4)

C(41) 92(6) 123(8) 111(8) -77(7)

C(42) 31(5) 67(7) 410(20) 77(10)

C(43) 47(4) 75(6) 91(6) 12(5)

C(44) 84(6) 57(6) 80(6) -15(5)

C(45) 68(5) 51(5) 92(6) -20(4)

C(46) 32(3) 30(4) 34(4) 9(3)

C(47) 41(3) 37(4) 39(4) 3(3)

C(48) 53(4) 47(4) 37(4) 2(3)

C(49) 53(4) 43(4) 30(4) -8(3)

C(50) 42(4) 65(5) 68(5) -13(4)

C(51) 46(4) 46(5) 71(5) 9(4)

254

C(52) 49(4) 57(5) 74(5) -6(4)

C(53) 60(4) 57(5) 23(4) -8(3)

C(54) 28(3) 36(4) 28(3) -1(3)

C(55) 22(3) 31(4) 37(4) 4(3)

C(56) 77(6) 66(6) 73(6) 4(5)

C(57) 36(3) 57(5) 41(4) 0(4)

C(58) 41(4) 46(4) 41(4) 21(3)

C(59) 50(4) 30(4) 67(5) 14(3)

C(60) 39(4) 46(5) 50(4) 15(3)

C(61) 36(4) 41(4) 38(4) 4(3)

C(62) 32(4) 43(4) 41(4) -6(3)

C(63) 24(3) 47(4) 36(4) -2(3)

C(64) 52(4) 77(6) 69(5) -13(5)

C(65) 30(3) 34(4) 32(4) 1(3)

C(66) 28(3) 33(4) 23(3) 1(3)

C(67) 33(3) 34(4) 32(4) 3(3)

C(68) 33(3) 29(4) 33(4) 12(3)

C(69) 28(3) 29(4) 36(4) 9(3)

C(70) 43(4) 39(4) 43(4) 6(3)

C(71) 33(3) 36(4) 67(5) 8(3)

C(72) 33(3) 32(4) 59(4) 0(3)

C(73) 38(4) 41(4) 88(5) -3(4)

C(74) 103(7) 69(6) 140(8) 0(6)

255

C(75) 41(4) 40(4) 51(4) -10(3)

C(76) 29(3) 29(4) 38(4) 10(3)

C(77) 27(3) 31(4) 30(3) 10(3)

C(79) 34(3) 35(4) 20(3) 4(3)

C(80) 36(3) 37(4) 29(3) 13(3)

C(81) 64(4) 66(5) 40(4) 1(4)

C(82) 99(6) 61(6) 64(5) -14(4)

C(83) 96(8) 54(6) 106(9) -19(6)

C(84) 65(6) 39(5) 95(7) 5(5)

C(85) 108(8) 241(14) 109(9) 82(9)

C(86) 67(5) 57(6) 99(7) 27(6)

C(87) 53(5) 61(6) 78(7) 10(5)

C(88) 72(6) 97(8) 85(7) 35(6)

B(1) 17(3) 25(4) 19(4) -4(3)

B(2) 33(4) 61(6) 27(4) -10(4)

B(3) 23(3) 27(4) 18(4) -6(3)

B(4) 15(3) 39(4) 18(4) 2(3)

B(5) 25(3) 39(4) 18(4) 0(3)

B(6) 22(3) 22(4) 15(3) -4(3)

B(7) 16(3) 39(4) 26(4) 1(3)

B(8) 22(3) 30(4) 23(4) -1(3)

B(9) 37(4) 43(5) 26(4) -5(4)

B(10) 26(3) 36(4) 29(4) 1(3)

256

Li(1) 30(5) 41(6) 20(5) 7(4)

Li(2) 29(5) 32(6) 44(6) 4(5)

Li(3) 30(5) 32(6) 36(6) 3(5)

Li(4) 30(5) 36(6) 18(5) -1(4)

Table C.20: Hydrogen coordinates (x 104) and isotropic displacement parameters (Å2 x

103) for U.

______

x y z U(eq)

______

H(1A) 8273 4075 5209 174

H(1B) 7892 3761 5369 174

H(2A) 7214 2171 4165 164

H(2B) 7121 2752 3580 164

H(3A) 11117 2595 5503 174

H(3B) 10938 3769 5284 174

H(3C) 11352 3418 5232 174

H(4A) 8284 4852 6014 136

H(4B) 7882 5465 5723 136

H(4C) 8264 5780 5563 136

H(5A) 10161 8406 3740 83

H(5B) 9735 7976 3708 83

H(5C) 9789 8842 3266 83

257

H(6A) 10124 7511 2914 60

H(6B) 10069 6646 3355 60

H(7A) 9392 4828 1303 98

H(7B) 9278 6002 1488 98

H(7C) 8961 5044 1330 98

H(8A) 9318 4044 2101 67

H(8B) 9636 5005 2259 67

H(9A) 9097 8292 2857 55

H(10A) 8557 9252 2916 61

H(11A) 8042 8319 3060 55

H(14A) 7517 7105 2602 60

H(15A) 6972 6302 2745 66

H(16A) 7044 5045 3437 63

H(17A) 6566 2002 3689 176

H(17B) 6521 3305 3642 176

H(17C) 6615 2722 4230 176

H(22A) 11071 2078 4659 105

H(22B) 10658 2426 4711 105

H(23A) 9537 1719 3686 82

H(23B) 9909 2175 4152 82

H(23C) 9961 1269 3726 82

H(24A) 9752 2515 3016 65

H(24B) 9700 3421 3441 65

258

H(25A) 7942 500 5380 47

H(26A) 7867 1381 6141 54

H(27A) 8318 2654 6614 48

H(29A) 10416 4274 2800 42

H(30A) 10664 5564 2327 45

H(31A) 11057 6979 2796 43

H(35A) 9619 -145 4410 107

H(35B) 9170 -447 4144 107

H(35C) 9435 -1149 4649 107

H(36A) 9501 383 5227 57

H(36B) 9235 1086 4722 57

H(39A) 8389 -1392 4212 49

H(39B) 8047 -574 3891 49

H(40A) 7788 -2340 3944 94

H(40B) 7613 -1483 4280 94

H(40C) 7954 -2298 4601 94

H(41A) 3265 4734 -238 154

H(41B) 3008 3834 -59 154

H(42A) 2130 2934 -817 228

H(42B) 2176 2369 -1352 228

H(43A) 1579 2120 -1290 111

H(43B) 1555 2834 -1825 111

H(43C) 1509 3415 -1287 111

259

H(44A) 5302 8478 -1239 128

H(44B) 4863 8101 -1327 128

H(44C) 4964 8870 -1772 128

H(45A) 2816 -2539 -1323 103

H(45B) 2601 -1676 -1043 103

H(45C) 2953 -2394 -669 103

H(47A) 3726 2900 1872 43

H(48A) 4108 4284 2411 50

H(49A) 4388 5607 1997 48

H(50A) 3932 7464 -728 95

H(50B) 3648 6637 -551 95

H(50C) 4086 6282 -488 95

H(51A) 4313 7623 182 66

H(51B) 3874 7979 119 66

H(52A) 5379 8195 1410 87

H(52B) 4951 8712 1232 87

H(52C) 5060 7780 862 87

H(53A) 5129 6508 1576 58

H(53B) 5020 7441 1946 58

H(91A) 7140 274 3483 96

H(57A) 5221 6710 -1538 60

H(57B) 5322 7478 -1984 60

H(58A) 4272 8232 -2221 53

260

H(59A) 3714 9224 -2270 61

H(60A) 3162 8302 -2223 55

H(61A) 2666 7177 -2707 49

H(62A) 2084 6479 -2643 51

H(63A) 2085 5167 -1987 45

H(64A) 3231 5070 610 101

H(64B) 2767 5145 381 101

H(64C) 3029 6044 204 101

H(70A) 3103 2681 1175 47

H(71A) 2677 1399 645 51

H(72A) 2825 470 -56 49

H(73A) 4201 1083 -485 62

H(73B) 4439 418 53 62

H(74A) 4643 -65 -683 145

H(74B) 4211 -432 -1020 145

H(74C) 4448 -1097 -482 145

H(75A) 3388 -1468 -1047 54

H(75B) 3034 -747 -1423 54

H(81A) 4469 5664 -3324 70

H(81B) 4126 6293 -3171 70

H(82A) 3868 5024 -3864 130

H(82B) 3759 4687 -3323 130

H(82C) 4101 4061 -3477 130

261

H(90A) 7703 1232 3438 125

H(89A) 7941 963 2715 93

H(85A) 7572 -842 1637 227

H(85B) 7986 -539 2061 227

H(85C) 7713 406 1712 227

H(86A) 6847 -947 2765 96

H(87A) 7108 -1188 2054 85

Table C.21: Crystal data and structure refinement for B.2

Identification code B.2

Empirical formula C32 H30 Cl2 O2 P2 C32 H30 Cl2 O2 P2

Formula weight 579.40

Temperature 170 K

Wavelength 0.71073 Å

Crystal system Monoclinic

Space group P2(1)/c

262

Unit cell dimensions a = 11.091(5) Å α= 90.00°

b = 12.572(5) Å β= 99.322(6)°

c = 10.360(4) Å γ = 90.00°

Volume 1425.5(10) Å3

Z 2

Density (calculated) 1.350 g/cm3

Absorption coefficient 0.369 mm-1

Theta range for data collection 1.86 to 25.00°

Index ranges -43<=h<=43, -14<=k<=14, -26<=l<=30

Reflections collected 98952

Independent reflections 2519

Absorption correction Multi-scan

Max. and min. transmission 0.9434 and 0.9879

Refinement method Refinement of F2 against ALL reflections

Data / restraints / parameters 2519 / 0 / 174

Goodness-of-fit on F2 0.974

Final R indices [I>2sigma(I)] R1 = 0.0576, wR2 = 0.1462

Table C.22: Atomic coordinates (x 104) and equivalent isotropic displacement

parameters (Å2 x 103) for B.2. U(eq) is defined as one third of the trace of the

orthogonalized Uij tensor.

______

263

x y z U(eq)

______

P1 P 0.30626(11) -0.04666(10) 1.01728(13) 0.0306(4)

O1 O 0.4340(3) 0.1346(2) 0.9880(3) 0.0303(8)

C2 C 0 0.3214(4) 0.1432(4) 0.9086(4) 0.0281(11)

C7 C 0.2434(4) 0.0576(4) 0.9087(4) 0.0267(11)

C5 C 0.1017(4) 0.1439(4) 0.7397(4) 0.0293(11)

C6 C 0.1326(4) 0.0593(4) 0.8227(4) 0.0314(12)

H6 H 0.0777 0.0012 0.8214 0.038

C1 C 0.4566(4) 0.0298(3) 1.0433(4) 0.0277(12)

C3 C 0.2939(4) 0.2310(4) 0.8306(4) 0.0337(12)

H3 H 0.3481 0.2898 0.8341 0.040

C4 C 0.1835(4) 0.2296(4) 0.7466(5) 0.0354(13)

264

H4 H 0.1622 0.2891 0.6912 0.042

C8 C -0.0135(4) 0.1452(4) 0.6384(4) 0.0361(13)

H8 H -0.0585 0.0776 0.6488 0.043

C10 C 0.0174(5) 0.1456(5) 0.5010(5) 0.0606(17)

H10A H 0.0560 0.2133 0.4850 0.091

H10B H -0.0577 0.1366 0.4375 0.091

H10C H 0.0737 0.0870 0.4918 0.091

C9 C -0.0977(5) 0.2363(4) 0.6594(6) 0.0648(19)

H9A H -0.1185 0.2317 0.7476 0.097

H9B H -0.1725 0.2319 0.5947 0.097

H9C H -0.0565 0.3040 0.6494 0.097

265

C11 C 0.5186(4) 0.0412(4) 1.1835(4) 0.0289(11)

C14 C 0.6509(5) 0.0602(5) 1.4343(5) 0.0493(15)

H14 H 0.6979 0.0659 1.5192 0.059

C12 C 0.5737(4) 0.1372(4) 1.2269(5) 0.0359(13)

H12 H 0.5668 0.1968 1.1697 0.043

C16 C 0.5286(4) -0.0449(4) 1.2693(5) 0.0366(12)

H16 H 0.4895 -0.1102 1.2423 0.044

C13 C 0.6383(4) 0.1466(4) 1.3524(5) 0.0435(14)

H13 H 0.6738 0.2128 1.3818 0.052

C15 C 0.5952(4) -0.0356(4) 1.3935(5) 0.0446(14)

H15 H 0.6029 -0.0949 1.4511 0.054

Cl2 Cl 0.23354(11) -0.00420(10) 1.18358(12) 0.0424(4)

266

Table C.23: Bond lengths [Å] and angles [°] for B.2.

______

P1-C7 1.793(4)

P1-C1 1.906(5)

P1-Cl2 2.0866(19)

O1-C2 1.384(5)

O1-C1 1.442(5)

C2-C3 1.373(6)

C2-C7 1.381(6)

C7-C6 1.397(6)

C5-C6 1.375(6)

C5-C4 1.403(6)

C5-C8 1.516(6)

C6-H6 0.9500

C1-C11 1.509(6)

C1-C1 1.604(9)

C3-C4 1.382(6)

C3-H3 0.9500

C4-H4 0.9500

C8-C10 1.517(6)

C8-C9 1.515(6)

C8-H8 1.0000

267

C10-H10A 0.9800

C10-H10B 0.9800

C10-H10C 0.9800

C9-H9A 0.9800

C9-H9B 0.9800

C9-H9C 0.9800

C11-C16 1.394(6)

C11-C12 1.394(6)

C14-C13 1.371(7)

C14-C15 1.388(7)

C14-H14 0.9500

C12-C13 1.384(6)

C12-H12 0.9500

C16-C15 1.380(6)

C16-H16 0.9500

C13-H13 0.9500

C15-H15 0.9500

C7-P1-C1 87.8(2)

C7-P1-Cl2 99.66(16)

C1-P1-Cl2 101.56(15)

C2-O1-C1 112.9(3)

C3-C2-C7 123.3(4)

C3-C2-O1 120.3(4)

268

C7-C2-O1 116.3(4)

C2-C7-C6 118.2(4)

C2-C7-P1 113.0(3)

C6-C7-P1 128.7(4)

C6-C5-C4 117.9(4)

C6-C5-C8 122.5(4)

C4-C5-C8 119.5(4)

C5-C6-C7 121.1(4)

C5-C6-H6 119.5

C7-C6-H6 119.5

O1-C1-C11 108.6(3)

O1-C1-C1 106.6(4)

C11-C1-C1 111.2(4)

O1-C1-P1 108.2(3)

C11-C1-P1 115.8(3)

C1-C1-P1 106.0(4)

C2-C3-C4 116.7(4)

C2-C3-H3 121.6

C4-C3-H3 121.6

C3-C4-C5 122.8(4)

C3-C4-H4 118.6

C5-C4-H4 118.6

C10-C8-C5 110.9(4)

269

C10-C8-C9 111.7(5)

C5-C8-C9 112.3(4)

C10-C8-H8 107.2

C5-C8-H8 107.2

C9-C8-H8 107.2

C8-C10-H10A 109.5

C8-C10-H10B 109.5

H10A-C10-H10B 109.5

C8-C10-H10C 109.5

H10A-C10-H10C 109.5

H10B-C10-H10C 109.5

C8-C9-H9A 109.5

C8-C9-H9B 109.5

H9A-C9-H9B 109.5

C8-C9-H9C 109.5

H9A-C9-H9C 109.5

H9B-C9-H9C 109.5

C16-C11-C12 118.8(4)

C16-C11-C1 121.2(4)

C12 C11 C1 120.0(4)

C13-C14-C15 120.2(5)

C13-C14-H14 119.9

C15-C14-H14 119.9

270

C13-C12-C11 120.6(5)

C13-C12-H12 119.7

C11-C12-H12 119.7

C15-C16-C11 120.3(5)

C15-C16-H16 119.9

C11-C16-H16 119.9

C14-C13-C12 120.0(5)

C14-C13-H13 120.0

C12-C13-H13 120.0

C16-C15-C14 120.1(5)

C16-C15-H15 119.9

C14-C15-H15 119.9

Table C.24 Anisotropic displacement parameters (Å2x 103) for B.2. The anisotropic

displacement factor exponent takes the form: -2π2[ h2 a*2U11 + ... + 2 h k a* b* U12]

______

U11 U22 U33 U23 U13 U12

______

P1 0.0247(7) 0.0297(7) 0.0356(8) 0.0038(6) -0.0004(6) -0.0011(6)

O1 0.0246(18) 0.0251(19) 0.038(2) 0.0052(15) -0.0032(2) 0.0006(2)

C2 0.019(3) 0.035(3) 0.028(3) -0.002(2) -0.002(2) 0.003(2)

C7 0.025(3) 0.024(3) 0.029(3) 0.004(2) -0.002(2) -0.001(2)

C5 0.027(3) 0.028(3) 0.032(3) -0.002(2) 0.002(2) -0.001(2)

271

C6 0.032(3) 0.029(3) 0.032(3) -0.002(2) 0.002(2) 0.001(2)

C1 0.028(3) 0.025(3) 0.027(3) 0.000(2) -0.003(2) 0.004(2)

C3 0.028(3) 0.030(3) 0.042(3) -0.002(3) 0.002(2) -0.003(2)

C4 0.037(3) 0.031(3) 0.036(3) 0.005(2) 0.000(2) 0.006(2)

C8 0.037(3) 0.036(3) 0.032(3) 0.006(2) -0.005(2) 0.000(2)

C10 0.063(4) 0.083(5) 0.032(3) 0.012(3) -0.002(3) -0.021(3)

C9 0.043(4) 0.053(4) 0.086(5) -0.015(3) -0.026(3) 0.014(3)

C11 0.020(2) 0.037(3) 0.028(3) -0.004(2) 0.001(2) 0.002(2)

C14 0.039(3) 0.071(4) 0.034(3) -0.006(3) -0.004(3) 0.000(3)

C12 0.030(3) 0.038(3) 0.038(3) -0.003(3) 0.000(2) 0.003(2)

C16 0.033(3) 0.042(3) 0.034(3) 0.002(3) 0.002(2) -0.001(2)

C13 0.038(3) 0.050(4) 0.040(3) -0.015(3) -0.004(3) -0.004(3)

C15 0.038(3) 0.058(4) 0.036(3) 0.009(3) 0.000(3) 0.000(3)

Cl2 0.0372(8) 0.0487(9) 0.0422(8) 0.0069(7) 0 .0093(6) 0.0042(6)

272

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