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.

(POCN)Ni(ii) complexes were found to mediate a variety of carbonyl hydroboration reactions, including chemoselective hydroboration of benzaldehyde and hydroborative reduction of amides.

The commercially available and bench‐stable Co(acac)2 ligated with bis[(2‐diphenylphosphino)phenyl] ether (dpephos) was employed for selective room temperature hydroboration of nitro compounds with HBPin (TOF up to 4615 h−1), tolerating halide, hydroxy, amino, ether, ester, lactone, amide and heteroaromatic functionalities. These reactions offered a direct access to a variety of N‐borylamines RN(H)BPin, which were in situ treated with aldehydes and carboxylic acids to produce a series of aldimines and secondary carboxamides without the need for dehydrating and/or coupling reagents. Combination of these transformations in a sequential one‐pot manner allowed for direct and selective synthesis of aldimines and secondary carboxamides from readily available and inexpensive nitro compounds.

The aminophosphinite pincer complex (POCNH)NiBr was found to effectively catalyze transfer hydrogenation of aldehydes and ketones with 2-propanol and KOtBu as a base, presenting a rare example of bifunctional nickel...