Bakewell, ClareClareBakewellWhite, Andrew JPAndrew JPWhiteCrimmin, Mark RMark RCrimmin2018-07-192019-05-022018-05-28Angewandte Chemie International Edition, 2018, 57 (22), pp.6638-66421521-3757http://hdl.handle.net/10044/1/60994A series of industrially relevant fluoroalkenes react with a monomeric AlI complex. These reactions break strong sp2 and sp3 C-F bonds, and result in the formation of a diverse array of organoaluminium compounds. Mechanistic studies show that two mechanisms are likely in operation: 1) direct oxidative addition of the C-F bond to AlI occurs with retention of alkene stereochemistry, and 2) stepwise formation and decomposition of a metallocyclopropane intermediate occurs with inversion of alkene stereochemistry. As part of this mechanistic analysis, we have isolated the first aluminium metallocyclopropane complex from oxidative addition of an alkene to AlI . Remarkably this reaction is reversible and reductive elimination of the alkene occurs at higher temperature reforming AlI . Furthermore, in selected cases the organoaluminium products are susceptible toward β-fluoride elimination to yield a double C-F activation pathway.© 2018 Wiley‐VCH Verlag GmbH & Co. KGaA, Weinheim. This is the accepted version of the following article: C. Bakewell, A. J. P. White, M. R. Crimmin, Angew. Chem. Int. Ed. 2018, 57, 6638, which has been published in final form at https://dx.doi.org/10.1002/anie.201802321HFOsaluminumfluoride eliminationfluoroolefinshydrofluorocarbonsJournal Articlehttps://www.dx.doi.org/10.1002/anie.201802321https://onlinelibrary.wiley.com/doi/full/10.1002/anie.2018023211521-3773