Hydroboration and Hydrosilylation of a Molybdenum-Nitride Complex Bearing a PNP-Type Pincer Ligand

Hydroboration and hydrosilylation of a molybdenum-nitride complex, prepared from the direct cleavage of the bridging dinitrogen coordinated to the two molybdenum atoms of a dinitrogen-bridged dimolybdenum complex, with pinacolborane and diphenylsilane give the corresponding borylimide-hydride and silylimide-hydride complexes, respectively. DFT calculations support a proposed reaction pathway of hydroboration toward the molybdenum-nitride complex to afford the corresponding borylimide-hydride complex. The reaction of the molybdenum-nitride complex with an excess amount of catecholborane under atmospheric nitrogen gas affords up to 2 equiv of ammonia based on the molybdenum atom after hydrolysis of the reaction mixture. This result indicates that a superstoichiometric reaction to afford the corresponding borylamine proceeds via hydroboration of a molybdenum-nitride complex as a key step.