Room-temperature reaction of carbon monoxide with a stable diarylgermylene.

Reactions of the heteroleptic diarylgermylenes GeAr(#)(Ar') (1) or GeAr(#) (Ar*-3,5-Pr(i)(2)) (2) (Ar(#) = C(6)H(3)-2,6-(C(6)H(2)-2,4,6-Me(3))(2); Ar' = C(6)H(3)-2,6-(C(6)H(3)-2,6-Pr(i)(2))(2); Ar*-3,5-Pr(i)(2) = C(6)H-2,6-(C(6)H(2)-2,4,6-Pr(i)(3))(2)-3,5-Pr(i)(2)) with carbon monoxide at room temperature gave alpha-germyloxy ketones via double CO insertion into the Ge-Ar' carbon bond in 1 and the Ge-Ar(#) bond in 2. The Ar(#)Ge-OCC(O)Ar' and 3,5-Pr(i)(2)Ar*Ge-O-CC(O)Ar(#) intermediates that are formed are unstable and rearrange via the insertion of the carbon of the GeOC moiety into a methyl-aryl or isopropyl carbon to form six-membered ring products.