title: Iridium phosphinidene complexes: a comparison with iridium imido complexes in their reaction with isocyanides.
abstract: 18-Electron nucleophilic, Schrock-type phosphinidene complexes 3 [Cp*(Xy-N[triple bond]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[triple bond]C) IrPAr C=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[triple bond]Nt-Bu] 1.
authors.affiliation: Department of Chemistry and Pharmaceutical Sciences, Vrije Universiteit Amsterdam, De Boelelaan 1083, 1081 HV, Amsterdam, The Netherlands.
authors.forename: Halil
authors.initials: H
authors.lastname: Aktas
authors.forename: Jos
authors.initials: J
authors.lastname: Mulder
authors.forename: Frans J J
authors.initials: FJ
authors.lastname: de Kanter
authors.forename: J Chris
authors.initials: JC
authors.lastname: Slootweg
authors.forename: Marius
authors.initials: M
authors.lastname: Schakel
authors.forename: Andreas W
authors.initials: AW
authors.lastname: Ehlers
authors.forename: Martin
authors.initials: M
authors.lastname: Lutz
authors.forename: Anthony L
authors.initials: AL
authors.lastname: Spek
authors.forename: Koop
authors.initials: K
authors.lastname: Lammertsma
mesh_terms: D003486:Cyanides / Q000737:chemistry*; D004583:Electrons; D007094:Imides / Q000737:chemistry*; D007495:Iridium / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry*; D010720:Phosphines / Q000737:chemistry*; D011789:Quantum Theory
chemical_list: D003486:Cyanides; D007094:Imides; D009942:Organometallic Compounds; D010720:Phosphines; D007495:Iridium