5-heptanedionato)nickel(II) (1c) as versatile hydrosilylation catalyst precursors is described. Complexes 1a-c catalyze 1,4-selectivehydrosilylation of 1,3-dienes in the presence of NaBHEt3 at ambient temperature. The reactions exhibit good regioselectivity to give the branched isomers as major products. The catalytic system also catalyzes hydrosilylation of alkenes including industriary important siloxy-
feedstock isoprene with unactivated silanes has been developed using earth‐abundant iron catalysts. The manipulation of regioselectivity relies on fine modification of the coordination geometry of the iron center. While a bidentate pyridine imine ligand promoted the formation of allylic silanes through 4,1‐addition, selectivity for the 3,4‐adduct homoallylic silanes was observed with a tridentate nitrogen