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.