NHC‐Stabilized Bis(trimethylsilyl)phosphido Complexes of Pd^II and Ni^II

Abstract

Abstract Halidometal complexes bearing monodentate N‐heterocyclic carbenes [MX 2 (R 2 ‐bimy) 2 ] {bimy = benzimidazole‐2‐ylidene; R = i Pr, M = Pd or Ni, X = I; R = n Bu, M = Pd, X = I and R = n Bu, M = Ni, X = Br ( 1 )} react under mild conditions with Li[P(SiMe 3 ) 2 ], in a 1:1 ratio, to provide the halido(silylphosphido)metal complexes [PdI( i Pr 2 ‐bimy) 2 {P(SiMe 3 ) 2 }] ( 2 ), [PdI( n Bu 2 ‐bimy) 2 {P(SiMe 3 ) 2 }] ( 3 ), [NiI( i Pr 2 ‐bimy) 2 {P(SiMe 3 ) 2 }] ( 4 ) and [NiBr( n Bu 2 ‐bimy) 2 {P(SiMe 3 ) 2 }] ( 5 ). Cleavage of the P–Si bonds in 3 and 5 with benzoyl chloride leads to the formation of the new (dibenzoylphosphido)halidometal complexes [PdI( i Pr 2 ‐bimy) 2 P{C(O)Ph} 2 ] ( 6 ) and [NiI( i Pr 2 ‐bimy) 2 {P(C(O)Ph) 2 }] ( 7 ), respectively. NMR spectroscopy, X‐ray crystallography and mass spectrometry are used to analyze these coordination complexes.