Structural Characterization and Unique Catalytic Performance of Silyl-Group-Substituted Geminal Dichromiomethane Complexes Stabilized with a Diamine Ligand
datasetposted on 16.08.2017, 00:00 by Masahito Murai, Ryuji Taniguchi, Naoki Hosokawa, Yusuke Nishida, Hiroko Mimachi, Toshiyuki Oshiki, Kazuhiko Takai
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.