Iridium phosphinidene complexes: a comparison with iridium imido complexes in their reaction with isocyanides.
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.
Aktas
Halil
H
Department of Chemistry and Pharmaceutical Sciences, Vrije Universiteit Amsterdam, De Boelelaan 1083, 1081 HV, Amsterdam, The Netherlands.
Mulder
Jos
J
de Kanter
Frans J J
FJ
Slootweg
J Chris
JC
Schakel
Marius
M
Ehlers
Andreas W
AW
Lutz
Martin
M
Spek
Anthony L
AL
Lammertsma
Koop
K
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
D003486:Cyanides; D007094:Imides; D009942:Organometallic Compounds; D010720:Phosphines; D007495:Iridium