Cooperative Bond Activation by a Bimetallic Main-Group Complex

Inspired by natural metalloenzymes that efficiently catalyze a variety of transformations, chemists have developed large numbers of dinuclear transition-metal complexes with extraordinary properties and reactivity patterns. For main-group element compounds, however, metal–metal cooperativity is much less explored. Here we present the synthesis and characterization of a room-temperature-stable compound with two separated two-coordinated gallium­(I) centers possessing both a lone pair of electrons and a vacant orbital, reminiscent of singlet carbenes. This species displays enhanced reactivity compared to its mononuclear counterpart due to bimetallic cooperativity that allows for the facile activation of strong C–F bonds across the gallium–gallium bond. Two mechanistic scenarios of the cooperative bond activation have been identified by DFT and DLPNO-CCSD­(T) calculations.