690229-26-6Relevant articles and documents
Transition metal coordination and reactivity of 2-(azidomethyl)-, 2-(chloromethyl)- and 2-(iodomethyl)phenyl isocyanides
Basato, Marino,Facchin, Giacomo,Michelin, Rino A.,Mozzon, Mirto,Pugliese, Sandra,Sgarbossa, Paolo,Tassan, Augusto
, p. 349 - 356 (2008/10/09)
2-(Azidomethyl)phenyl isocyanide, 2-(CH2N3)C 6H4N≡C (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(I) species such as [AuCl(AziNC)] (3), derived from the reaction of [AuCl(Me 2S)] 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 PPh 3 affording the phosphinimine-isocyanide derivatives [M(CO) 5{C≡NC6H4-2-(CH2N=PPh 3)}] (M=W (5), Cr (6)). Complex 6 reacts with H2O affording a mixture of the amino-isocyanide [Cr(CO)5{C≡NC 6H4-2-(CH2NH2)}] (7) and the carbene [Cr(CO)5{CN(H)C6H4-2-CH 2N(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][BF 4] (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 MeNH 2 to afford in low yield the N-heterocyclic carbene species [W(CO)5{CN(H)C6H4-2-CH2N(Me)}] (13).
