Journal article

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

Marius Deuker, Yang Yang, Richard AJ O'Hair, Konrad Koszinowski

ORGANOMETALLICS | AMER CHEMICAL SOC | Published : 2021

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..

View full abstract

University of Melbourne Researchers

Grants

Awarded by Deutsche Forschungsgemeinschaft


Awarded by ARC


Funding Acknowledgements

K.K. thanks Mr. Thomas Auth for helpful discussions. M.D. and K.K. gratefully acknowledge support from the Deutsche Forschungsgemeinschaft (KO 2875/12). R.A.J.O. acknowledges the support of the ARC (DP180101187) and the National Computing Infrastructure. Y.Y. is grateful to the University of Melbourne for the support of a PhD scholarship.