Diazo Decomposition and Carbene Transfer Mediated by a Pincer Gold(III) Complex

The pincer triflimide Au(III) complex (N∧C∧C)AuNTf2 2 is shown to decompose aryl diazo compounds Ph2CN2, (Dmp)CN2H (Dmp = 2,6-dimesitylphenyl), and (p-F3CPh)CN2H and generate the corresponding Au(III) carbene complexes. Azine compounds resulting from carbene/diazo coupling have been isolated and structurally characterized. Carbene transfer to external reagents such as trimethylsilyl azide, methanol, and styrene affords the corresponding imine, ether, and cyclopropane under both stoichiometric and catalytic conditions.