The Reactivity of Germanium Phosphanides with Chalcogens

The reactivity of germanium phosphanido complexes with elemental chalcogens is reported. Addition of sulfur to [(BDI)­GePCy2] (BDI = CH­{(CH3)­CN-2,6-iPr2C6H3}2) results in oxidation at germanium to form germanium­(IV) sulfide [(BDI)­Ge­(S)­PCy2] and oxidation at both germanium and phosphorus to form germanium­(IV) sulfide dicylohexylphosphinodithioate complex [(BDI)­Ge­(S)­SP­(S)­Cy2], whereas addition of tellurium to [(BDI)­GePCy2] only gives the chalcogen inserted product, [(BDI)­GeTePCy2]. This reactivity is different from that observed between [(BDI)­GePCy2] and selenium. Addition of selenium to the diphenylphosphanido germanium complex, [(BDI)­GePPh2], results in insertion of selenium into the Ge–P bond to form [(BDI)­GeSePCy2] as well as the oxidation at phosphorus to give [(BDI)­GeSeP­(Se)­Ph2]. In contrast, addition of selenium to the bis­(trimethylsilyl)­phosphanido germanium complex, [(BDI)­GeP­(SiMe3)2], yields the germanium­(IV) selenide [(BDI)­Ge­(Se)­P­(SiMe3)2].