Insertion of isonitrile into the Mo–C bond of [MoCp2(CH3)(CNH)]+: a density functional study

Abstract

The reaction of CNH with the methyl group in the transition metal complex [MoCp₂(CH₃)CNH]⁺, to form a η²-iminoacyl complex, was theoretically investigated with density functional methods. The geometries of the reactant, transition state, and product complexes were optimized at the LDA level, and then GGA single point calculations were performed on these optimized structures. The transition state for the reaction, automatically generated, has some product-like character, as the new C–C bond has partially formed, and it indicates that the mechanism consists of a methyl migration to the carbon of the isonitrile, acompanied by a reorganization of the isonitrile. The activation energy (E_a) and the reaction energy (ΔE) were calculated to be 15.9 and −14.8 kcal mol⁻¹, respectively.