Neutral, Cationic and Hydride-substituted Siloxygermylenes.

The introduction of the labile trimethylsiloxy group to Ge centers in the presence of an N-heterocyclic carbene donor is reported. The new complex IPr⋅GeCl(OSiMe ) (IPr=[(HCNDipp) C:]; Dipp=2,6-iPr C H ) was readily converted into the structurally unique Ge siloxy(hydrido)germylene IPr⋅GeH(OSiMe )⋅BH by treatment with lithium borohydride. Additionally, the reactive siloxygermylene cation [IPr⋅Ge(OSiMe )] was synthesized and clean oxidative addition of CH Cl was demonstrated. The two-coordinate [IPr⋅Ge(OSiMe )] cation also promoted the catalytic hydroborylation of sterically hindered ketones under mild conditions, with enhanced reactivity stemming from an open coordination site at Ge.