Synthesis of Cyclometalated Gold(III) Complexes via Catalytic Rhodium to Gold(III) Transmetalation

Angew Chem Int Ed Engl. 2022 May 9;61(20):e202116755. doi: 10.1002/anie.202116755. Epub 2022 Mar 16.

Abstract

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 multistep transmetalation from rhodium to gold as the underlying 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.

Keywords: (C^N)Gold(III) Complexes; Cycloauration; Gold(III); Rhodium; Transmetalation.