A series of industrially relevant fluoroalkenes react with a monomeric Al(I) complex. These reactions break either strong sp2 or sp3 CâF bonds and result in the formation of a diverse array of organoaluminium compounds. Mechanistic studies show that two mechanisms are likely in operation: Oxidative addition of the CâF bond to Al(I) occurs with retention of alkene stereochemistry, while stepwise formation and decomposition of a metallocyclopropane intermediate occurs with inversion of alkene stereochemistry. As part...