The first thioether complexes of the hard Lewis acidic GeF4 and SnF4 have been prepared by reaction of [GeF4(MeCN)2] or [SnF4(MeCN)2] respectively with the thioether ligand in rigorously anhydrous CH2Cl2 solution. The isolated compounds were characterised spectroscopically (IR, 1H and 19F{1H} NMR) and by microanalyses. Crystal structures of four representative examples, [GeF4{MeS(CH2)2SMe}], [GeF4{EtS(CH2)2SEt}], [SnF4{EtS(CH2)2SEt}] and [SnF4{iPrS(CH2)2SiPr}], reveal distorted octahedral adducts with chelating thioethers, and weak, secondary Ge–S and Sn–S bonds. These compounds are the first reported examples of thioether complexes with any main group metal/metalloid fluoride acceptor.
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