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.
ASJC Scopus subject areas
- Colloid and Surface Chemistry