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

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.