A Thesis Submitted for the Degree of PhD at the University of Warwick Permanent WRAP URL: http://wrap.warwick.ac.uk/90802 Copyright and reuse: This thesis is made available online and is protected by original copyright. Please scroll down to view the document itself. Please refer to the repository record for this item for information to help you to cite it. Our policy information is available from the repository home page. For more information, please contact the WRAP Team at: [email protected] warwick.ac.uk/lib-publications Reactions and Co-ordination Chemistry of Indium Trialkyls and Trihalides. Ian Alan Degnan A thesis submitted for the degree of Doctor of Philosophy. University of Warwick, Department of Chemistry. Septem ber 1989 To Mam and Dad -for making this possible. Contents. Page. Chapter 1: Introduction. Group 13 Elements. 4 Co-ordination Chemistry of the Indium Trihalides. 9 Mono-Complexes of Indium Trihalides. 10 Bis-Complexes of Indium Trihalides. 12 Tris-Complexes of Indium Trihalides. 17 Unusual Indium Trihalide Complexes. 20 Phosphine Complexes of Indium Triiodide. 22 Metathetical Reactions of Indium Trihalides. 30 Organometallic Derivatives of Indium. 33 Organoindium Halides. 33 Organoindium Compounds. 37 Reactions of Organoindium Compounds. 39 Control of Oligomerisation in Indium Compounds. 55 Chapter 2. Phosphine Complexes of Indium Trihalides. 58 Introduction. 59 Mono-Phosphine Complexes of Indium Triiodide. 60 X-ray Diffraction Study of InCI3(PMe3)2. 83 Indium Triiodide Complexes of Diphos. 86 Chapter 3. Metathetical Reactions of Indium Trihalides. 94 Introduction. 95 Reaction of Indium Triiodide Phosphine Complexes with Methyllithium. 96 Reaction of Indium Triiodide Triphenylphosphine Complex with Methyllithium. 97 Reaction of Indium Triiodide Di-t-butylphosphine Complex with Methyllithium. 102 Reaction of Indium Trihalides with Phosphidolithium Compounds. 111 Reaction of Indium Triiodide with Di-t-butylphosphidolithium. 113 Chapter 4. Reactions of Trialkylindium Compounds with Species Containing Protonic Hydrogens. 121 Introduction. 122 Reactions of Trimethyl and Triethylindium with Compounds Containing Protonic Hydrogens. 125 Conclusions. ISS Contents. (Cont'd) Page. Chapter 5. Thermal Decomposition of Organoindium Compounds. 160 Introduction. 161 Thermal Decomposition of [(Et2InPBut2h]. 162 Appendix A. Indium-Phosphorus Bond Lengths. 170 Appendix B. X -Ray Crystallographic Studies. 179 Appendix C. Experimental. 215 Appendix D. Mass Spectra. 233 References. 244 ii Diagrams and Tables. Chapter I. Page Diagram 1. Molecular Structure of In2I6. 5 Diagram 2. It-Bonding in Boron Trihalides. 7 Table 1. Mono-Complexes of Indium Trihalides. 11 Table 2. Bis-Complexes of Indium Trihalides. 13 Diagram 3. Molecular Structure of InCI3(NMe3)2. 15 Table 3. Tris-Complexes of Indium Trihalides. 18 Diagram 4. Molecular Structure of InCI3PY 4. 19 Diagram 5. Molecular Structure of [(lnCI3h(Me3AsO)3]. 21 Table 4. Phosphine Complexes of Indium Triiodide. 23 Table 5. Raman Data of Indium-Iodine Compounds. 26 Table 6. I: I Phosphine Complexes of Indium Triiodide. 29 Diagram 6. Metathetical Reactions of Indium Halides. 31 Table 7. Co-ordination Compounds of Organoindium Halides. 36 Diagram 7. Molecular Structure of Et1nI2(TMEDA). 37 Diagram 8. Molecular Structure of 2.2.6.6.-Tetramethyl­ piperidine Complex with Trimethylindium. 38 Table 8. Reactions of Organoindium Compounds with Compounds Containing Protonic Hydrogens. 44 Diagram 9. Structure of Pyridine-2-carbaldehyde Oxime Derivative of InMe3. 53 Diagram 10. Molecular structure of the Tetramethyl- oxamidine Derivative of Trimethylindium. 53 Diagram 11. Molecular structure of [(Me3SiCH2hInPPh212. 56 Chapter 2. Diagram 1. Molecular Structure of [InI3(But2PH)]. 62 Diagram 2. Packing Diagram for Structure of [lnI3(But2PH)]. 63 Diagram 3. Interactions between two Molecules of [lnI3(But2PH)]. 6S Table 1. Raman Data of 1: 1 Indium Triiodide-Phosphine Complexes. 67 Diagram 4. Raman Spectra of 1: 1 Indium Triiodide-Phosphine Complexes. 68 Diagram 5. Molecular Structure of [InI3(Ph2PH)]. 70 iii Page. Diagram 6. Packing Diagram for Structure of [InI3(Ph2PH)). 71 Diagram 7. Interactions between three molecules of [InI3(Ph2PH»). 72 Table 2. pKa Values of Phosphines. 74 Table 3. 31 P-N.m.r. Data of InI3PR3 Complexes. 75 Diagram 8. 31P-N.m.r. Spectra of InI3PBui3 Complex. 77 Diagram 9. 31 P-N.m.r. Spectra of InI3(PBut2H) Complex. 79 Table 4. 11SIn-N.m.r. Data of InI3PR3 Complexes. 81 Diagram 10. Molecular Structure of InCI3(PMe3h. 84 Table 5. Infra-red Data of Indium Triiodide-Diphos Adducts. 87 Diagram 11. Molecular Structure of (lnI3h(Diphos}J. 88 Diagram 12. Interactions between two Molecules of (lnI3h( Di phos}J. 89 Diagram 13. Proposed Structure of [InI3(Diphos)]. 92 Diagram 14. Proposed Structure of [InI3(Diphoshl. 93 Chapter 3. Table 1. 1 H-N.m.r. Data of Methyl Derivatives of [lnI3.PPh31. 98 Diagram 1. Fragmentation Scheme for Mass Spectrum of [MelnI2.PPh3l. 99 Diagram 2. Ligand Exchange Fragmentation Scheme for Mass Spectrum of [MeInI2.PPh3). 99 Diagram 3. Fragmentation scheme for mass spectrum of [Mc2InI.PPh3). 100 Diagram 4. Ligand Exchange Fragmentation Scheme for Mass Spectrum of [Me2InI.PPh31. 101 Table 2. 1H-N.m.r. Data of Methyl Derivatives of [l3In.HPBut21. 104 Table 3. Thermal Stability of [I3In.HPBut21 Derivatives. 106 Diagram 5. Fragmentation Scheme for Mass Spectrum of [MeInI2.But2PH] . 107 Diagram 6. Fragmentation Scheme for Mass Spectrum of [Me2InI.But2PH] . 108 iv Pa ge. Diagram 7. Proposed Structures of [MelnI2.But2PH] and [Me2InI.But2PH]. 110 Diagram 8. Molecular Structure of Anion of [Li(THF)4 ][In(PPh2)41. 112 Diagram 9. Molecular Structure of [In(PBut2)31. 116 Diagram 10. Molecular Structure of [In(PBut2)31. 117 Diagram 11. Space filling Model of [In(PBut2hl. 119 Chapter 4. Diagram 1. In-C Vibrational Modes of InMe3. 123 Diagram 2. Relationship between Infra-red Spectra and InC2 Bond Angles. 124 Table 1. Reactions of Trialkylindium with Protonic Species. 125 Diagram 3. Molecular Structure of [(Et2InPBut2hl. 128 Diagram 4. Molecular Structure of [(Et2InPBut2hl. 129 Table 2. Bond Lengths and Angles for [(Et2InPBut2hl and [(Me2InPBut2)21. 130 Table 3. E. I. Mass Spectrum Data of [(Et2InPBut2hl. 131 Diagram S. Infra-red Spectrum of [(Et2InPBut2hl. 133 Diagram 6. Molecular Structure of [(Me2In(Sal)hl. 135 Table 4. E. I. Mass Spectrum Data of [(Me2In(Sal)hl. 137 Table S. E. I. Mass Spectrum Data of 2-Carboxy- benzaldehyde Derivative of InMe3. 141 Diagram 7. Proposed Structure of 2-Carboxy­ benzaldehyde Derivative of InMe3. 142 Table 6. E. I. Mass Spectrum Data of 2-Pyrrolidinone Derivative of InMe3. 144 Diagram 8. Possible Structures for 2-Pyrrolidinone Derivative of InMe3. 144 Diagram 9. Proposed Structure of 2-Pyrrolidinone Derivative of InMe3. 146 Table 7. E.I. Mass Spectrum Data of the Diphenyl­ acetamidine Derivative of InMe3. 148 Diagram 10. Proposed Structure of Dipbenyl- acetamidine Derivative of InMe3. 149 v Pa gee Table 8. E.1. Mass Spectrum Data of the Ethanolamine Derivative of JnEt3. 152 Diagram 11. Proposed Structure of Diethyl(phenylelhynyl)- Indium Triphenylphosphine Adduct. 154 Table 9. Infra-red Spectra of Organo­ Indium Compounds. 156 Diagram 12. Possible Free Radical Pathway for Reactions with Trialkylindium. 158 CbiUUs:[ ~. Diagram 1. Reaction Scheme for the Thermal Decomposition of (Me2GaAsBut2h. 162 Diagram 2. O. C. Trace of Hydrocarbons. 164 Table I. E. I. Mass Spectra Data of Hydrocarbons. 165 Diagram 3. Decomposition Pathways for (Et2InPBut2h. 166 Diagram 4. Proposed Mechanism for the Formation of But2PPBut2. 168 Appendjx A. Table 1. In-P Bond Lengths. 171 Diagram I. Group Orbitals of Phosphorus in Trigonal Bipyramidal Complex. 174 Diagram 2. Bonding Interactions with Phosphorus Group Orbitals. 175 Diagram 3. Simplified Molecular Orbital Diagram. 177 Appendix B. Table 1. Bond Lengths of Compound 1*. 187 Table 2. Bond Angles of Compound I. 187 Table 3. Atomic Co-ordinates of Compound 1. 188 Table 4. Bond Lengths of Compound 2. 190 Table S. Bond Angles of Compound 2. 190 Table 6. Atomic Co-ordinates of Compound 2. 191 Table 7. Bond Lengths of Compound 3. 193 Table 8. Bond Angles of Compound 3. 194 vi Pa gee Table 9. Atomic Co-ordinates of Compound 3. 195 Table 10. Bond Lengths of Compound 4. 197 Table 11. Bond Angles of Compound 4. 197 Table 12. Atomic Co-ordinates of Compound 4. 198 Table 13. Bond Lengths of Compound 5. 200 Table 14. Bond Angles of Compound 5. 201 Table 15. Atomic Co-ordinates of Compound 5. 202 Table 16. Bond Lengths of Compound 6. 204 Table 17. Bond Angles of Compound 6. 205 Table 18. Atomic Co-ordinates of Compound 6. 207 Diagram 1. Three Molecules of [In(PBut2)3] in the Unit Cell. 209 Table 19. Bond Lengths of Compound 7. 211 Table 20. Bond Angles of Compound 7. 211 Table 21. Atomic Co-ordinates of Compound 7. 212 Diagram 2. Unit Cell of Compound 7. 213 *Compound 1 = InCI3(PMe3>2 Compound 2 =InI3.HPBut2 Compound 3 =(InI3h(Diphos)3 Compound 4 =[(Me2InSal)2] Compound 5 =InI3·HPPh2 Compound 6 = In(PBut2h Compound 7 = (Et2InPBu12h Appendix C. Table 1. Infra-red data of the 13In.PR3 complexes. 222 Table 2. Infra-red Data of InI3.PR3 (But2PH and PPh3). 226 vii Ack now I ed Kernen ts I I would like to the following people whose help and support over the last three years has been invaluable: Prof. M. G. H, Wallbridge. for the constant help and advice without which this work would not have been possible. Dr. Alan Berzins and Dr. Alan Boardman of the Johnson Matthey Technology Centre (Sonning Common) for their help. S. M. Roe. Dr. N. W. Alcock and Dr. H. R. Powell for help and tuition in the mysteries of X -ray crystallography. Also Prof. G. M. Sheldrick and Dr. M. McPartlin for their contributions. Dr. O. W, Howarth and J. Lall for their help in obtaining the n.m.r. spectra reported in this work. Mr.