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Solid-phase Synthesis of [4.4] Spirocyclic Oximes
Published on: February 6, 2019
Neutral Silylyne Complex of Molybdenum: Synthesis, Properties, and Access to Silaiminoacyl Complexes via [2+3]
Hisako Hashimoto1, Kohei Watanabe1, Takashi Yoshimoto1
1Department of Chemistry, Graduate School of Science, Tohoku University, 6-3 Aoba-ku, Sendai, 980-8578, Japan.
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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