Facile CH Bond Formation by Reductive Elimination at a Dinuclear Metal Site

The electronically unsaturated dirhenium complex [Re2(CO)8(µ‐AuPPh3)(µ‐Ph)] (1) was obtained from the reaction of [Re2(CO)8{µ‐η2‐C(H)C(H)nBu}(µ‐H)] with [Au(PPh3)Ph]. The bridging {AuPPh3} group was replaced by a bridging hydrido ligand to yield the unsaturated dirhenium complex [Re2(CO)8(µ‐H)(µ‐Ph)] (2) by reaction of 1 with HSnPh3. Compound 2 reductively eliminates benzene upon addition of NCMe at 25 °C. The electronic structure of 2 and the mechanism of the reductive elimination of the benzene molecule in its reaction with NCMe were investigated by DFT computational analyses.