Kong, Richard YRichard YKongCrimmin, Mark RMark RCrimmin2020-06-302021-06-262020-07-15Journal of the American Chemical Society, 2020, 142 (28), pp.11967-119710002-7863http://hdl.handle.net/10044/1/80276Aluminum(I) and magnesium(I) compounds are reported for the C–C σ-bond activation of strained alkylidene cyclopropanes. These reactions result in the formal addition of the C–C σ-bond to main group center either at a single site (Al) or across a metal–metal bond (Mg–Mg). Mechanistic studies suggest that rather than occurring by a concerted oxidative addition, these reactions involve stepwise processes in which substrate binding to the main group metal acts as a precursor to α- or β-alkyl migration steps that break the C–C σ-bond. This mechanistic understanding is used to develop the magnesium-catalyzed hydrosilylation of the C–C σ-bonds of alkylidene cyclopropanes.© 2020 American Chemical Society. This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of the American Chemical Society, after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/jacs.0c0338303 Chemical SciencesGeneral ChemistryJournal Articlehttps://www.dx.doi.org/10.1021/jacs.0c03383https://pubs.acs.org/doi/10.1021/jacs.0c033831520-5126