title: Synthesis and DFT Study of a Diphenylsilanone-Bridged Dimolybdenum Complex.
abstract: Reaction of the 30-electron benzylidyne complex [Mo2 Cp2 (μ-CPh)(μ-PCy2 )(μ-CO)] with excess Ph2 SiH2 under visible-UV irradiation yields the silylene-bridged complex [Mo2 Cp2 (μ-CPh)(μ-PCy2 )(μ-SiPh2 )]. This compound undergoes selective oxidation with O2 to give the unsaturated complex [Mo2 Cp2 (μ-CPh)(μ-PCy2 )(μ-κ(1) :κ(1) -OSiPh2 )], which contains an unprecedented bridging diphenylsilanone ligand, as confirmed by X-ray diffraction analysis and DFT calculations. The bonding within the central Mo2 SiO ring of this complex approaches the extreme description of a dimetallacyclosiloxane according to the relevant solid-state bond lengths and theoretical calculations.
authors.affiliation: Departamento de Química Orgánica e Inorgánica/IUQOEM, Universidad de Oviedo, C/Julian Clavería, 8, 33071, Oviedo, Spain.
authors.forename: M Angeles
authors.initials: MA
authors.lastname: Alvarez
authors.affiliation: Departamento de Química Orgánica e Inorgánica/IUQOEM, Universidad de Oviedo, C/Julian Clavería, 8, 33071, Oviedo, Spain.
authors.forename: M Esther
authors.initials: ME
authors.lastname: García
authors.affiliation: Departamento de Química Orgánica e Inorgánica/IUQOEM, Universidad de Oviedo, C/Julian Clavería, 8, 33071, Oviedo, Spain. garciavdaniel@uniovi.es.
authors.forename: Daniel
authors.identifier: http://orcid.org/0000-0002-2441-2486
authors.initials: D
authors.lastname: García-Vivó
authors.affiliation: Departamento de Química Orgánica e Inorgánica/IUQOEM, Universidad de Oviedo, C/Julian Clavería, 8, 33071, Oviedo, Spain.
authors.forename: Sonia
authors.initials: S
authors.lastname: Menéndez
authors.affiliation: Departamento de Química Orgánica e Inorgánica/IUQOEM, Universidad de Oviedo, C/Julian Clavería, 8, 33071, Oviedo, Spain. mara@uniovi.es.
authors.forename: Miguel A
authors.initials: MA
authors.lastname: Ruiz
keywords: metal-metal bonds; metallacycles; molybdenum; silanones; silylene