Alvarez M Angeles, García M Esther, García-Vivó Daniel, Menéndez Sonia, Ruiz Miguel A
Departamento de Química Orgánica e Inorgánica/IUQOEM, Universidad de Oviedo, C/Julian Clavería, 8, 33071, Oviedo, Spain.
Chemistry. 2016 Jun 20;22(26):8763-7. doi: 10.1002/chem.201601598. Epub 2016 May 13.
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.
