Neutral, Cationic and Hydride‐substituted Siloxygermylenes

Abstract

Abstract The introduction of the labile trimethylsiloxy group to Ge II centers in the presence of an N‐heterocyclic carbene donor is reported. The new complex IPr⋅GeCl(OSiMe 3 ) (IPr=[(HCNDipp) 2 C:]; Dipp=2,6‐ i Pr 2 C 6 H 3 ) was readily converted into the structurally unique Ge II siloxy(hydrido)germylene IPr⋅GeH(OSiMe 3 )⋅BH 3 by treatment with lithium borohydride. Additionally, the reactive siloxygermylene cation [IPr⋅Ge(OSiMe 3 )] + was synthesized and clean oxidative addition of CH 2 Cl 2 was demonstrated. The two‐coordinate [IPr⋅Ge(OSiMe 3 )] + cation also promoted the catalytic hydroborylation of sterically hindered ketones under mild conditions, with enhanced reactivity stemming from an open coordination site at Ge.