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-