Computational study of alkynes insertion into metal-hydride bonds catalyzed by bimetallic complexes

Density Functional Theory investigations on the insertion mechanism of phenylacetylene into metal-hydride bonds in bimetallic (Pt,Os) catalysts have been carried out. The results obtained have been also compared with the non-reactive monometallic (Os-based) system, to elucidate the cooperative effects and to explain the observed absence of reactivity. The identified reaction path involves phenylacetylene coordination followed by the insertion into the metal-hydride bond, leading to the formation of the experimentally observed products. Both steps do not require large energies compatible with the experimental conditions. The comparison with the reaction path for the monometallic species gives some hints on the cooperative effects due to the presence of the second metal which is related to its role in the CO release for creating a coordination site for phenylacetylene and not in the insertion energetics. The calculations provide a detailed analysis of the reaction complexity and provide a rationale for the efficiency of the process.