Selective Reduction of CO₂ to a Formate Equivalent with Heterobimetallic Gold‐ ‐ ‐Copper Hydride Complexes

A series of heterobimetallic complexes containing three‐center, two‐electron Au−H−Cu bonds have been prepared from addition of a parent gold hydride to a bent d 10 copper(I) fragment. These highly unusual heterobimetallic complexes represent a missing link in the widely investigated series of neutral and cationic coinage metal hydride complexes containing Cu−H−Cu and M−H−M + moieties (M=Cu, Ag). The well‐defined heterobimetallic hydride complexes act as precatalysts for the conversion of CO 2 into HCO 2 Bpin with HBpin as the reductant. The selectivity of the heterobimetallic complexes for the catalytic production of a formate equivalent surpasses that of the parent monomeric Group 11 complexes.