Synthesis, structures and reactivity of novel germanium(ii) aryloxide and arylsulfide complexes

Abstract

The protonolysis reactions between Ge[N(SiMe₃)₂]₂ and substituted phenols give rise to new germanium(II) aryloxide complexes [Ge(OAr)₂]_n (n = 2, ArO = OC₆H₂Me₃-2,4,6 1 or OC₆H₃ⁱPr₂-2,6 2; n = 1, ArO = OC₆H₃Ph₂-2,6 3 or OC₆HPh₄-2,3,5,6 4). The solid state structures of 1–4 have been determined by X-ray diffraction and compared to their spectroscopic properties. Compounds 1 and 2 contain bridging aryloxide ligands and the environment about the germanium atoms is pyramidal. Compound 1 reacts with benzil to yield a five-coordinate germanium complex [Ge(OC₆H₂Me₃-2,4,6)(O₂C₂Ph₂)(O₂C₂HPh₂)] 5, while compound 4 reacts with the same reagent to give [Ge(OC₆HPh₄-2,3,5,6)₂(O₂C₂Ph₂)] 6. The X-ray crystal structures of 5 and 6 have also been determined. Compound 4 also undergoes an oxidative addition reaction with CH₃I to yield the germane [Ge(OC₆HPh₄-2,3,5,6)₂(Me)(I)] (7). A novel arylsulfidegermane, [HGe(SC₆H₂ⁱPr₃-2,4,6)₃] 8, was isolated in the reaction between Ge[N(SiMe₃)₂]₂ and HSC₆H₂ⁱPr₃-2,4,6 and was characterized by NMR spectroscopy and an X-ray crystal structure.