Synthesis and DFT Study of a Diphenylsilanone-Bridged Dimolybdenum Complex

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• 作者：Dr. M. Angeles Alvarez ; Prof. Dr. M. Esther Garcí ; a ; Dr. Daniel Garcí ; a-Vivó ; Dr. Sonia Mené ; ndez and Prof. Dr. Miguel A. Ruiz
• 刊名：Chemistry - A European Journal
• 出版年：2016
• 出版时间：June 20, 2016
• 年：2016
• 卷：22
• 期：26
• 页码：8763-8767
• 全文大小：754K
• ISSN：1521-3765

文摘

Reaction of the 30-electron benzylidyne complex [Mo₂Cp₂(μ-CPh)(μ-PCy₂)(μ-CO)] with excess Ph₂SiH₂ under visible-UV irradiation yields the silylene-bridged complex [Mo₂Cp₂(μ-CPh)(μ-PCy₂)(μ-SiPh₂)]. This compound undergoes selective oxidation with O₂ to give the unsaturated complex [Mo₂Cp₂(μ-CPh)(μ-PCy₂)(μ-κ¹:κ¹-OSiPh₂)], which contains an unprecedented bridging diphenylsilanone ligand, as confirmed by X-ray diffraction analysis and DFT calculations. The bonding within the central Mo₂SiO ring of this complex approaches the extreme description of a dimetallacyclosiloxane according to the relevant solid-state bond lengths and theoretical calculations.