A catalytic method to synthesize a broad array of cyclometalated (C^N)gold(III) complexes is reported here. An unprecedented Rh-to-AuIII transmetalation allows the facile transfer of (C^N) ligands between these two metals in a redox-neutral process. The reaction employs commercially available precursors and proceeds under mild and environmentally benign conditions. Both experimental and computational studies support a multi- step transmetalation from rhodium to gold as the under- lying mechanism for these transformations. This process involves first, a rate-determining transfer of the C ligand followed by the subsequent incorporation of the N donor to form the monocyclometalated (C^N)gold(III) species.

The Department of Chemistry and the Forschungskredit (FK-20-118) of the University of Zurich are acknowledged for financial support. We thank the Spanish Ministerio de Ciencia, Innovación y Universidades (PID 2019-110008GB-I00).