CC reductive coupling mediated by attack at a spectator ligand

•Reductive coupling of bis(alkynyl) complex to a diyne complex.•Solvent-mediated reaction involving attack at ancillary carbonyl ligand.•Proposed mechanism supported by kinetic measurements and computational study.

The alkynyl ligands in the iridium(III) complex [Cp*Ir(CO)(CCPh)2] undergo reductive coupling to form the diyne complex [Cp*Ir(CO)(PhCCCCPh)]. This process is assisted by nucleophilic attack at the carbonyl ligand by the solvent.

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