The Reactivity of Germanium Phosphanides with Chalcogens.

The reactivity of germanium phosphanido complexes with elemental chalcogens is reported. Addition of sulfur to [(BDI)GePCy] (BDI = CH{(CH)CN-2,6-iPrCH}) results in oxidation at germanium to form germanium(IV) sulfide [(BDI)Ge(S)PCy] and oxidation at both germanium and phosphorus to form germanium(IV) sulfide dicylohexylphosphinodithioate complex [(BDI)Ge(S)SP(S)Cy], whereas addition of tellurium to [(BDI)GePCy] only gives the chalcogen inserted product, [(BDI)GeTePCy]. This reactivity is different from that observed between [(BDI)GePCy] and selenium. Addition of selenium to the diphenylphosphanido germanium complex, [(BDI)GePPh], results in insertion of selenium into the Ge-P bond to form [(BDI)GeSePCy] as well as the oxidation at phosphorus to give [(BDI)GeSeP(Se)Ph]. In contrast, addition of selenium to the bis(trimethylsilyl)phosphanido germanium complex, [(BDI)GeP(SiMe)], yields the germanium(IV) selenide [(BDI)Ge(Se)P(SiMe)].