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.

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An operationally simple hydrosilylation of alkenes is developed using a stable Fe(II)‐precatalyst with in situ activation by iPr2NEt.