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

Abstract

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.