Abstract
Addition of H2 across the cobalt–phosphorus bond of (PPP)CoPMe3 (3) is demonstrated, where PPP is a monoanionic diphosphine pincer ligand with a central N‐heterocyclic phosphido (NHP−) donor. The chlorophosphine CoII complex (PPClP)CoCl2 (2) can be generated through coordination of the chlorophosphine ligand (PPClP, 1) to CoCl2. Subsequent reduction of 2 with KC8 in the presence of PMe3 generates (PPP)CoPMe3 (3), in which both the phosphorus and cobalt centers have been reduced. The addition of 1 atm of H2 to complex 3 cleanly affords (PPHP)Co(H)PMe3 (4), in which H2 has ultimately been added across the metal–phosphorus bond. Complex 4 was characterized spectroscopically and using computational methods to predict its geometry.