The CO migratory insertion into M–O and M–C bonds of the new model (PMe3)2M(η2 – CH2CH2O) ( M = Ni , Pd and Pt ) (model (d)) proposed in this work has been studied with the aid of density functional theory (DFT) calculations. It is found (1) when M = Ni , CO migratory insertion into Ni–C is thermodynamically and kinetically favored, and (2) when M = Pd and Pt , the insertion into M–O bond via a one-step process is preferred. Further investigation on CO migratory insertion using Pt(PMe3)2(C7H10O) (R′-Pt) derived from the experimental compound Pt(PEt3)2(C7H10O) gives the same conclusions as model (d) with M = Pt . Results obtained from the reaction of model (d) ( M = Pt ) with CO are consistent with the experimental observation that CO prefers to insert into Pt–O bond of Pt(PEt3)2(C7H10O) .
Migratory insertion reactions of nickel and palladium σ-alkyl complexes with a phosphinito-imine ligand