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

Author:

Hashimoto Hisako1ORCID,Watanabe Kohei1,Yoshimoto Takashi1,Hayakawa Naoki2,Matsuo Tsukasa2ORCID,Tobita Hiromi1ORCID

Affiliation:

1. Department of Chemistry Graduate School of Science Tohoku University 6-3 Aoba-ku Sendai 980-8578 Japan

2. Department of Applied Chemistry Faculty of Science and Engineering Kindai University 3-4-1 Kowakae Higashi Osaka 577–850 Japan

Abstract

AbstractA 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.

Publisher

Wiley

Subject

General Chemistry,Catalysis,Organic Chemistry

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