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Stabilisation of Heavier Carbene Analogues with Bulky Phosphides and Related Systems

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Stabilisation of Heavier Carbene Analogues with Bulky Phosphides and Related Systems Stabilisation of heavier carbene analogues with bulky phosphides and related systems by Peter Evans A thesis submitted in partial fulfilment of the requirements for the degree of Doctor of Philosophy Newcastle University September 2018 Abstract An array of monodentate alkali metal phosphides was prepared, for use as precursors to diphosphatetrylenes. Treatment of (Dipp)2PH (111) with either nBuLi, PhCH2Na or PhCH2K in THF gives [(Dipp)2P]Li(THF)3 (128a), {[(Dipp)2P]Na(THF)2}2 (129a) and [(Dipp)2P]K(THF)4 (130a), respectively; the alternative adduct [(Dipp)2P]Na(PMDETA) (129c) was prepared by the treatment of 129a with PMDETA. Treatment of either (Dipp)(Mes)PH (109) or (Dipp){(Me3Si)2CH}PH (113) with nBuLi gives [(Dipp)(Mes)P]Li(THF)3 (131a) and [(Dipp){(Me3Si)2CH}P]Li(THF)3 (134), respectively. Treatment of (Mes)2PH (108) with nBuLi gives [(Mes)2P]Li(THF)3 (132a) after recrystallization from n-hexane or the alternative solvate [(Mes)2P]2Li2(THF)2(OEt2) (132b) after recrystallization from Et2O. Exposure of compounds 128a, 129a, 130a, 131a, 132a and 132b to vacuum leads to the loss of coordinated solvent, yielding the alternative solvates [(Dipp)2P]Li(THF)2 (128b), [(Dipp)2P]Na(THF)2]1.5 (129b), [(Dipp)2P]K (130b), 7 [(Dipp)(Mes)P]Li(THF)2 (131b) and [(Mes)2P]Li(THF) (132c). Variable-temperature Li and 31P{1H} NMR spectroscopy indicates that 128b, 129b, 131b and 134 are subject to a monomer-dimer equilibrium in solution, while 132c is subject to a dynamic equilibrium between a dimer and cyclic trimer in solution. An array of diphosphatetrylenes was prepared by reactions between two equivalents of the corresponding lithium phosphides discussed above and the group 14 dihalide. In the solid- state, compounds {(Dipp)2P}2Sn (104Sn), {(Tripp)2P}2Ge∙(C7H14) (145Ge∙(C7H14)) and [{(Me3Si)2CH}2P]2Sn (148Sn) are stabilised by π interactions from a planar phosphorus centre, while {(Tripp)2P}2Sn (145Sn), {(Dipp)(Mes)P}2Ge∙(C6H14)0.5 (146Ge∙(C6H14)0.5), {(Dipp)(Mes)P}2Sn (146Sn) and [(Dipp){(Me3Si)2CH}P]2Sn (147Sn) adopt the alternative configuration with two pyramidal phosphorus centres, which stabilises the tetrel centre with 31 1 up to two short Ge/Sn∙∙∙Cipso contacts. Variable-temperature P{ H} NMR spectroscopy indicates that 104Sn, 145Ge and 145Sn are subject to a dynamic equilibria in solution, which interconverts between the planar and pyramidal centre and between two possible configurations. The reaction between two equivalents of [(Mes)2P]K and GeCl2(1,4-dioxane) in THF initially gives a blue solution of the putative diphosphagermylene {(Mes)2P}2Ge (160Ge). However, this solution degrades after three days at room temperature to the diphosphine (Dipp)2P-P(Dipp)2 (150) and the tetranuclear Ge(I) cluster [{(Mes)2P}Ge]4 (162). i Treatment of {(Mes)2P}2SiHCl (174) with either (Me3Si)2NLi or TMPLi gives a mixture of unidentified products. The reaction between {(Mes)2P}2SiCl2 (175) and lithium or potassium metal gives the corresponding alkali metal phosphide [(Mes)2P]M [M = Li, K] as the major product, although a small number of crystals of the potassium triphosphasilanate [{(Mes)2P}3Si]K(THF)3 (177∙THF) were isolated from the reaction with the potassium phosphide and characterised by X-ray crystallography. The reaction between four equivalents of [(Mes)2P]Li and SiBr4 in Et2O gives the tetraphosphadisilene {(Mes)2P}2Si=Si{P(Mes)2}2 (181). The reaction between two equivalents of [(Dipp)2P]K and either SiHCl3 or SiCl4 gives {(Dipp)2P}2SiHCl (189) or {(Dipp)2P}2SiCl2 (190), respectively, as impure mixtures. Compound 189 proved to be inert towards a range of strong bases, while the reduction of 190 with lithium or potassium metal in THF gives (Dipp)2P-P(Dipp)2 (150). Treatment of the base stabilised dichlorosilylene [{CH2N(Dipp)}2C]SiCl2 (191) with two equivalents of [(Dipp)2P]K gives the phosphasilene {(Dipp)2P}Si(Dipp){P(Dipp)} (192), rather than the corresponding diphosphasilylene, due to a 1,2-aryl migration. The diphosphaarsenium cation [{(Dipp)2P}2As][Al{OC(CF3)3}4] (208) was prepared by the reaction between {(Dipp)2P}2AsCl (205) and Li[Al{OC(CF3)3}4] in fluorobenzene. In the solid-state, compound 208 is stabilised by a π interaction from a planar phosphorus centre, while in solution a dynamic equilibrium is in operations, which interconverts the planar and pyramidal phosphorus centres, similarly to the diphosphagermylenes 104Ge and 145Ge. The reaction between {(Mes)2P}2PCl (213) and Na[B{3,5-(CF3)2C6H3}4] in fluorobenzene gives the cyclic diphosphaphosphonium salt [{μ-(Mes)P}2P(Mes)2][B{3,5- (CF3)2C6H3}4] (216). Compound 216 arises from a 1,2-aryl migration of the putative + diphosphaphosphenium cation {(Mes)2P}2P , followed by a cyclization. The reaction between two equivalents of [(Dipp)2As]Li and GeCl2(1,4-dioxane) or SnCl2 gives {(Dipp)2As}2Ge∙C7H8 (234Ge) and {(Dipp)2As}2Sn∙C7H8 (234Sn), respectively. Compounds 234Ge and 234Sn each adopt a configuration with two pyramidal arsenic centres in the solid state and are stabilised by two short Ge/Sn∙∙∙Cipso contacts. A series of bidentate lithium phosphides were prepared, for use as potential precursors to P-heterocyclic tetrylenes. Treatment of CH2(PHDipp)2 (246) with two equivalents of nBuLi, followed by TMEDA gives [CH2(PLiDipp)2](TMEDA)2 (257). Treatment of {CH2PHDipp)2 (253) with two equivalents of nBuLi gives the solvate ii {CH2(PLiDipp)}2(THF)(OEt2)1.5 (258b), from this material the alternative solvate {CH2(PLiDipp)}2(THF)(OEt2) (258a) was characterised by X-ray crystallography. Treatment of DippPH(CH2)nPHDipp [n = 3 (254), 4 (255), 5 (256)] with two equivalents of nBuLi in THF gives [CH2{CH2(PLiDipp)}2(THF)4 (259), {CH2CH2(PLiDipp)}2(THF)6 (260) and [CH2{CH2CH2P(Dipp)}2]Li2(THF)6(C7H8) (261a). Compound 261a rapidly loses coordinated solvent on exposure to vacuum, yielding the alternative solvate [CH2{CH2CH2(PLiDipp)}2](THF)2.5 (261b). Compounds 258b, 259, 260 and 261b exhibit complex variable-temperature 31P{1H} and 7Li NMR behaviour indicating dynamic equilibria between monomeric and oligomeric species in solution. The reaction between {CH2(PLiDipp)}2 and SnCl2 gives [{CH2(PDipp)}2Sn]2 (cis/trans-265) as a mixture of cis and trans stereoisomers, while the reaction between [CH2{CH2(PLiDipp)}2 and SnCl2 gives the cis stereoisomer of [CH2{CH2(PDipp)}2Sn]2 (cis- 266c). The solvates [{CH2(PDipp)}2Sn]2.Et2O (trans-265a), [CH2{CH2(PDipp)}2Sn]2.(THF)2 (cis-266b) and [CH2{CH2(PDipp)}2Sn]2.(THF)3 (cis-266c) were characterised by X-ray crystallography. iii iv Acknowledgements There are several people who I wish to thank for helping me produce this piece of work. In particular, I am very grateful to my supervisor Dr Keith Izod for his continued support and guidance in both the production of this thesis and in the laboratory over the past four years. I would also like to thank Dr. Corinne Wills and Professor William McFarlane for their guidance and expertise with NMR spectroscopy, and to Dr. Paul. G. Waddell for his patience and care with my samples for X-ray crystallography. I would also like to thank members of the research group, past and present, for their help and advice in the laboratory. In particular, thanks to Dr. Claire Jones, Atheer Al- Rammahi and Dr. Casey Dixon. Finally, I would like to say a huge thank you to my family and friends for their support over the past few years, in particular, to my parents Maureen and Paul, to whom I dedicate this thesis. v vi Publications from this work Chapter 3 Desolvation and aggregation of sterically demanding alkali metal diarylphosphides. K. Izod, P. Evans, P. G. Waddell, Dalton Trans., 2017, 46, 13824. Chapter 4 Remote substituent effects on the structures and stabilities of P=E π-stabilized diphosphatetrylenes (R2R)2E (E = Ge, Sn). K. Izod, P. Evans, P. G. Waddell, M. R. Probert, Inorg. Chem. 2016, 55, 10510. Chapter 6 A fully phosphane-substituted disilene. K. Izod, P. Evans, P. G. Waddell, Angew. Chem. Int. Ed. 2017, 56, 5593. Chapter 10 A diarsagermylene and a diarsastaannylene stabilised by arene∙∙∙Ge/Sn interactions. K. Izod, P. Evans, P. G. Waddell, Chem. Comm., 2018, 2526. Chapter 11 and 12 Influence of Chain Length on the Structures and Dynamic Behavior of Alkyl-Tethered α,ω- Diphosphide Complexes of Lithium and Their Use in the Synthesis of P-Heterocyclic Stannylenes, K. Izod, P. Evans, T. H. Downie, W. McFarlane, P. G. Waddell, Inorg. Chem., 2018, 57, 14733. List of Abbreviations Å angstrom Ppm parts per million br broad PMDETA N,N,N′,N′′,N′′- Cp cyclopentadienyl pentamethyldiethylenetriamine Cp* pentamethylcyclopentadienyl q quartet d doublet s singlet Dep 2,6-diisoethylphenyl t triplet Dipp 2,6-diisopropylphenyl Tripp 2,4,6-triisopropylphenyl Hz hertz TMEDA N,N,N′,N′- Mes 2,4,6-trimethylphenyl tetramethylethylenediamine Mes* 2,4,6-tritertbutylphenyl vii viii Table of important compounds 108 109 110 111 112 113 114 128a 129a 129c 130a 131a ix 132a 139 134 144 E = Ge (104Ge), Sn (104Sn) 145Ge 145Sn E = Ge (146Ge), Sn (146Sn) 147Sn 148Sn 150 161 162 174 175 M = Li (176), K (177) x 181 189 190 192 205 208 213 216 226 233 E = Ge (234Ge), Sn (234Sn) 246 253 254 255 256 257 258a 259 xi 260 261a cis-265 trans-265 cis-266 267 xii Table of Contents Abstract…………………………………………………………………………………….…...i Acknowledgements…………………………………...……………………….….……….…...v Publications from this work…………………...……………………………………………...vii List of Abbreviations…………………………………………….……………..…………….vii Table of important compounds………………………………………………………………..ix Chapter 1. Introduction .......................................................................................................... 1 1.1 Introduction to low-oxidation state group 14 compounds ..........................................
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