The synthesis and characterisation of complexes of tin and germanium fluorides with soft donor ligands

Abstract

The pseudooctahedral complexes [S11F4L2] (L = THF, pyridine, OPR3, OAsR3, PR3) and [SnF4{L-L}] (L-L = 2,2'-bipyridyl, 1,10-phenanthroline, MeO(CH2)2OMe, Me2N(CH2)2NMe2, R2P(O)CH2P(O)R2, o-C6H4(P(O)R2)2) R2P(CH2)2PR2, o-C6H4(PR2)2) have been prepared from [SnF4{MeCN}2] and the appropriate ligands in rigorously anhydrous CH2C12 solution. This includes the first phosphane and thioether complexes of the hard Lewis acid SnF4 and are the first reported examples of thioether complexes with any main group metal/metalloid fluoride acceptor. Attempts to prepare tertiary arsane complexes of SnF4 have been unsuccessful. Similar complexes of [GeF4{PR3}2] and [GeF4{L-L}] (L-L = R2P(CH2)2PR2 and o-C6H4(PR2)2) have also been prepared from [GeF4{MeCN}2] and the appropriate ligands in rigorously anhydrous CH2C12 solution. This includes the first phosphane and thioether complexes of the hard Lewis acid GeF4. In anhydrous CH2C12 solution the complexes are slowly converted into the corresponding phosphane oxide adducts by dry O2. The apparently contradictory literature on the reaction of GeCl4 with phosphanes is clarified. The complexes ?ra«s-[GeCl4{AsR3}2] (R = Me or Et) are obtained from GeCl4 and AsR3 either without solvent or in CH2C12. All the complexes have been characterised by microanalysis, Raman, IR, 'H, 31P{'H}, 19F{'H} and U9Sn NMR spectroscopy as appropriate. of The crystal structures phenanthroline} ], rrarcs-[SnF4{PCy3}2], ?rans-[SnF4{OPMe3}2], [SnF4 {MeO(CH2)2OMe} ], [SnF4{l,10- [SnF4 {o-C6H4(P(O)Ph2)2} ]-CH2Cl2-H2O, [SnF4{iPrS(CH2)2SiPr}], [SnF4{Et2P(CH2)2PEt2}], [SnCl4{Et2P(CH2)2PEt2}], [GeF4{o- C6H4(PMe2)2}], ?raMs-[GeCl4(AsEt3)2] and'Et3AsCl2 have been determined. Comparison of the structural and NMR spectroscopic data shows that SnF4 and GeF4 are the strongest Lewis acids in each series. [SnBr4{MeC(CH2AsMe2)3}], [GeF4{Ph2P(CH2)2PPh2}], [SnF4{EtS(CH2)2SEt}], This -Thesis also describes the attempted synthesis of a few tridentate arsane macrocycles as well as the synthesis and characterisation of their respective intermediaries. This included the facultative As2O-donors O{(CH2)2AsR2}2 (R = Me, Ph). They act as bidentate chelating As2-donors (L-L) in the distorted tetrahedral [M(L-L)2]BF4 (M = Cu or Ag). Representative crystal structures of [Ag(O{(CH2)2AsPh2}2)2]BF4-MeOH and [Cu(O{(CH2)2AsPh2}2)2]BF4-MeOH were .also obtained as well as the unexpected Cu(I)-Cu(I) complex, [Cu2{Me2As(CH2)2OH}3](BF4)2 of the fragmented ligand. >

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