2-(Azidomethyl)phenyl isocyanide, 2-(CH2N3)C6H4NC (AziNC), coordinates to {M(CO)5} (M = W, Cr) fragments to afford the corresponding isocyanide complexes [M(CO)5(AziNC)] (M = W (1), Cr (2)). AziNC coordinates also to some Au(1) species such as [AuCl(AziNC)] (3), derived from the reaction of [AuCl(Me2S)] with AziNC, and [Au(AziNC)2][BF4] (4), obtained from the reaction of 3 with AgBF4, followed by treatment with AziNC. Complexes 1 and 2 undergo the Staudinger reaction with PPh3 affording the phosphinimine-isocyanide derivatives [M(CO)5{CNC6H4-2-(CH2N=PPh3)}] (M = W (5), Cr (6)). Complex 6 reacts with H2O affording a mixture of the amino-isocyanide [Cr(CO)5{CNC6H4-2-(CH2NH2)}] (7) and the carbene [Cr(CO)5{CN(H)C6H4-2-CH2N(H)}] (8) species. Complexes 3 and 4 react with 1 or 2 equiv. of PPh3 displacing the isocyanide with the formation of the complexes [AuCl(PPh3)] (9) and [Au(PPh3)2][BF4] (10), respectively. The halogeno-isocyanide complexes [W(CO)5(CNC6H4-2-CH2Cl)] (11) and [W(CO)5(CNC6H4-2-CH2I)] (12) show different reactivity towards amines so that only 12 reacts with MeNH2 to afford in low yield the N-heterocyclic carbene species [W(CO)5{CN(H)C6H4-2-CH2N(Me)}] (13). (C) 2003 Elsevier Science B.V. All rights reserved.