title: Computational study of alkynes insertion into metal-hydride bonds catalyzed by bimetallic complexes.
abstract: 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.
authors.affiliation: Laboratoire d'Electrochimie, Chimie des Interfaces et Modélisation pour l'Energie, UMR CNRS 7575 ENSCP Chimie ParisTech 11, rue P. et M. Curie F-75231, Paris Cedex 05, France.
authors.forename: Stefania
authors.initials: S
authors.lastname: Di Tommaso
authors.forename: Vincent
authors.initials: V
authors.lastname: Tognetti
authors.forename: Emilia
authors.initials: E
authors.lastname: Sicilia
authors.forename: Carlo
authors.initials: C
authors.lastname: Adamo
authors.forename: Nino
authors.initials: N
authors.lastname: Russo
mesh_terms: D000480:Alkynes / Q000737:chemistry*; D002384:Catalysis; D056004:Molecular Dynamics Simulation; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D009992:Osmium / Q000737:chemistry*; D010984:Platinum / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D000480:Alkynes; D009942:Organometallic Compounds; D009992:Osmium; D010984:Platinum