Insertion of Nitriles Into a Gold(III)/Carbene Bond: A Direct and Powerful Entry to Imino‐Substituted Carbenes

Abstract Strikingly, very little is known so far about reactive gold(III) carbenes. They have been proposed as key intermediates in a few reactions but remain chemical curiosities. Taking into account the enhanced electrophilicity of cationic Au(III) carbene complexes, we were intrigued by their reactivity with nitriles. Thus, we discovered a simple and efficient entry to imino‐substituted carbenes. The transient (N^C^C)Au(III)←:CH(dmp) + carbene readily reacts with acetonitrile, benzonitrile, and diisopropyl cyanamide, affording stable and isolable Au(III) carbene complexes. Here, the imino group acts either as a strongly π‐donating or a spectator substituent. Ligand exchange at Au(III) or protodeauration/deprotonation provides access to the corresponding free species, which display dual imino‐carbene / nitrile‐ylide reactivity, as substantiated by stoichiometric and catalytic dimerization, O─H insertion and [3 + 2] cycloaddition reactions.