A Nucleophilic Gold(III) Carbene Complex

Anthony Pujol; Mathieu Lafage; Feriel Rekhroukh; Nathalie Saffon-Merceron; Abderrahmane Amgoune; Didier Bourissou; Noel Nebra; Marie Fustier-Boutignon; Nicolas Mézailles

doi:10.1002/anie.201706197

A Nucleophilic Gold(III) Carbene Complex

Angew Chem Int Ed Engl. 2017 Sep 25;56(40):12264-12267. doi: 10.1002/anie.201706197. Epub 2017 Aug 24.

Authors

Anthony Pujol¹, Mathieu Lafage¹, Feriel Rekhroukh¹, Nathalie Saffon-Merceron², Abderrahmane Amgoune¹, Didier Bourissou¹, Noel Nebra¹, Marie Fustier-Boutignon¹, Nicolas Mézailles¹

Affiliations

¹ Laboratoire Hétérochimie Fondamentale et Appliquée, Université Paul Sabatier/CNRS UMR 5069, 118 Route de Narbonne, 31062, Toulouse Cedex, France.
² Institut de Chimie de Toulouse ICT-FR2599, Université Paul Sabatier, 31062, Toulouse Cedex, France.

PMID: 28782276
DOI: 10.1002/anie.201706197

Abstract

The first Au^III carbene complex was prepared by reacting a geminal dianion with a (P,C) cyclometalated Au^III precursor. Its structure and bonding situation have been thoroughly investigated by experimental and computational means. The presence of a high-energy highest occupied molecular orbital (HOMO) centered at the carbene center suggests nucleophilic character for the Au^III carbene complex. This unprecedented feature was confirmed by reactions with two electrophiles (PhNCS and CS₂ ), resulting in two types of C=C coupling reactions.

Keywords: C=C coupling; carbene complexes; geminal dianions; gold(III); nucleophilic Schrock-type carbenes.

Publication types

Research Support, Non-U.S. Gov't