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Updated: Feb 24, 2026
Imine Metathesis by Silica-Supported Catalysts Using the Methodology of Surface Organometallic Chemistry
Published on: October 18, 2019
Structural Characterization and Unique Catalytic Performance of Silyl-Group-Substituted Geminal Dichromiomethane
Masahito Murai1, Ryuji Taniguchi1, Naoki Hosokawa1
1Division of Applied Chemistry, Graduate School of Natural Science and Technology, and ‡Research Institute for Interdisciplinary Science, Okayama University , 3-1-1 Tsushimanaka, Kita-ku, Okayama 700-8530, Japan.
Abstract:
Stabilization by a silyl group on the methylene carbon and a diamine ligand led to the isolation of gem-dichromiomethane species. X-ray crystallography confirmed the identity of the structure of this rare example of reactive gem-dimetalloalkane species. The isolated gem-dichromiomethane complex acted as a storable silylmethylidene carbene equivalent, with reactivity that could be changed dramatically upon addition of a Lewis acid (ZnCl2) and a base (TMEDA) to promote both silylalkylidenation of polar aldehydes and silylcyclopropanation of nonpolar alkenes. Identification of a key reactive species also identified the catalytic version of these transformations and provided insights into the reaction mechanism. In contrast to Simmons-Smith cyclopropanation, the real reactive species for the current cyclopropanation was a chromiocarbene species, not a chromium carbenoid species.
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