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Neutral Silylyne Complex of Molybdenum: Synthesis, Properties, and Access to Silaiminoacyl Complexes via [2+3] Cycloaddition

2023/09/25 by Hisako Hashimoto, Kohei Watanabe, Takashi Yoshimoto +3
Chemistry · #Catalytic Alkyne Reactions #Organometallic Complex Synthesis and Catalysis #Synthesis and characterization of novel inorganic/organometallic compounds

paper · pdf · doi:10.1002/chem.202302470

openalex publication_date 2023/09/25 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/30

Abstract

A neutral silylyne complex of molybdenum was synthesized by the stepwise dehydrogenation method and its properties were compared with those of the tungsten analog. The complex takes a dimeric form as crystals but afford a monomer-dimer equilibrium in solution. The replacement of the central metal from W to Mo led to a monomer dominant (~98 %) solution at room temperature. The monomer-dimer dynamics was investigated based on thermodynamic parameters. The molybdenum silylyne complex underwent [2+2] cycloaddition with alkynes much faster than the tungsten analog. The reactions with organic azides led to the formation of the first example of silaiminoacyl complexes through [2+3] cycloaddition. The structures and bonding aspects of the products were clarified by multiple measurements and DFT calculations.

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