The first examples of germanium tetrafluoride and tin tetrafluoride complexes with soft thioether coordination - synthesis, properties and crystal structures

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, H-1 and F-19{H-1}NMR) and by microanalyses. Crystal structures of four representative examples, [GeF4{MeS(CH2)(2)SMe}], [GeF4{EtS(CH2)(2)SEt}], [SnF4{EtS(CH2)(2)SEt}] and [SnF4{iPrS(H-2)(2)SiPr}], 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.