18-Electron nucleophilic, Schrock-type phosphinidene complexes 3 [Cp*(Xy-N≡C)Ir=PAr] (Ar = Mes*, Dmp, Mes) are capable of unprecedented [1 + 2]-cycloadditions with 1 equiv of isocyanide RNC (R = Xy, Ph) to give novel iridaphosphirane complexes [Cp*(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 [Cp*Ir=PAr] forming first complex 3 that subsequently reacts with another isocyanide to give the products following a different pathway than its nitrogen analogue [Cp*Ir≡Nt-Bu] 1. © 2009 American Chemical Society.
Aktas, H., Mulder, J. M., de Kanter, F. J. J., Slootweg, J. C., Schakel, M., Ehlers, A. W., ... Lammertsma, K. (2009). Iridium phosphinidene complexes: a comparison with iridium imido complexes in their reaction with isocyanides. Journal of the American Chemical Society, 131(37), 13531-7. https://doi.org/10.1021/ja9048509