LAUSR

The readily synthesized and bench‐stable cobalt dichloride complex (dpephos)CoCl2 is employed as a pre‐catalyst for a diversity of silane additions to unsaturated organic molecules, including the normally challenging reduction of amides to amines. With regard to hydrosilative reduction of amides even more effective and activator free catalytic systems can be generated from the bench‐stable, commercially available Co(acac)2 and Co(OAc)2 with dpephos and PPh3 ligands. These systems operate under mild conditions (<100 °C), with many examples of room temperature transformations, presenting a first example of mild cobalt‐catalyzed hydrosilylation of amides.