A DFT STUDY OF CO MIGRATORY INSERTION REACTIONS WITH A NEW TYPE OF GROUP 10 METAL-ALKYL AND METAL-ALKOXIDE BONDS

The CO migratory insertion into M-O and M-C bonds of the new model (PMe3)(2)M(eta(2) - 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).