As imple alkylamine[ ( iPr) 2 NEt] has been used to activate an air-a nd moisture-stable iron(II) pre-catalyst for alkene and alkyne hydrofunctionalization reactions.T his amine activation has enabled the highly operationallys imple hydrosilylation and hydroborationo fa lkenes and alkynes using just 0.25-2 mol% iron catalyst and 1-25 mol% amine. Significantly,t hese reactions proceedi ne qual yield under both air and inert reactionc onditions.

A precatalyst activation strategy has been developed for earth-abundant metal catalysis enabled by counterion dissociation and demonstrated through alkene hydroboration. Commercially available iron and cobalt tetrafluoroborate salts were found to catalyze the hydroboration of aryl and alkyl alkenes with good functional group tolerance (Fe, 12 substrates; Co, 13 substrates) with three structurally distinct ligands. Key to this endogenous activation was counterion dissociation to generate fluoride which indirectly activates the precatalyst by reaction with pinacol borane.

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Low oxidation-state iron- and cobalt catalysis has been enabled using tetrafluoroborate activation across 5 reaction classes and seven ligand frameworks using a single catalysis protocol.