Iridium Phosphinidene Complexes: A Comparison with Iridium Imido Complexes in Their Reaction with lsocyanides.

18-Electron nucleophilic, Schrock-type phosphinidene complexes 3 [Cpª(Xy—N≡C)lr=PAr] (Ar = Mesª, Dmp, Mes) are capable of unprecedented [1 + 2]-cycloadditions with 1 equiv of isocyanide RNC (R = Xy, Ph) to give novel iridaphosphirane complexes [Cpª(Xy—N≡C)IrPArC=NR]. Their structures were ascertaine...

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Detalles Bibliográficos
Publicado en:	Journal of the American Chemical Society Vol. 131; no. 37; pp. 13531 - 13538
Autores principales:	Aktas, Halil, Mulder, Jos, de Kanter, Frans J. J., Slootweg, J. Chris, Schakel, Marius, Ehlers, Andreas W., Lutz, Martin, Spek, Anthony L., Lammertsma, Koop
Formato:	Artículo
Publicado:	American Chemical Society 9/23/2009
Materias:	Iridium spectra Density functionals X-ray diffraction Isocyanides Nitrogen Nucleophilic reactions
Acceso en línea:	Ver este registro en EBSCOhost

Descripción
Sumario:	18-Electron nucleophilic, Schrock-type phosphinidene complexes 3 [Cpª(Xy—N≡C)lr=PAr] (Ar = Mesª, Dmp, Mes) are capable of unprecedented [1 + 2]-cycloadditions with 1 equiv of isocyanide RNC (R = Xy, Ph) to give novel iridaphosphirane complexes [Cpª(Xy—N≡C)IrPArC=NR]. Their structures were ascertained by X-ray diffraction. Density functional theory investigations on model structures revealed that the iridaphosphirane complexes are formed from the addition of the isocyanide to 16-electron species [Cpªlr=PAr] forming first complex 3 that subsequently reacts with another isocyanide to give the products following a different pathway than its nitrogen analogue [Cpªlr≡Nt-Bu] 1.