Tetraorganylargentate(III) Complexes: Key Intermediates in Silver-Mediated Cross-Coupling Reactions

Abstract

The use of silver as a catalyst in cross-coupling reactions remains underdeveloped. We show by means of electrospray-ionization mass spectrometry that the diorganylargentates LiAgR′2·Li(CN) (R′ = Me, Bu) formedin situreact with a wide scope of alkyl and aryl halides RX to afford the tetraorganylargentate(III) complexes R′3AgR-. Upon fragmentation in the gas phase, these high-valent species readily undergo reductive elimination. The trimethylorganylargentates Me3AgR-furnish the synthetically desired cross-coupling products MeR with high selectivity, whereas the tributylorganylargentates Bu3AgR-yield more of the homocoupling product Bu2. Quantum chemical calculations reproduce the experimental..