Catalytic Nitrogen Fixation via Direct Cleavage of Nitrogen-Nitrogen Triple Bond of Molecular Dinitrogen under Ambient Reaction Conditions

We have now found that molybdenum-iodide complexes bearing a PNP-pincer ligand have a higher catalytic activity than the so far reported molybdenum-dinitrogen complexes for ammonia formation from nitrogen gas under ambient reaction conditions, up to 830 equiv being produced based on a dinitrogen-bridged dimolybdenum complex (415 equiv of ammonia based on the molybdenum atom). This remarkable catalytic activity is induced by a novel reaction pathway, where the generation of a dinitrogen-bridged dimolybdenum-iodide complex is a key point to promote direct cleavage of the nitrogen-nitrogen triple bond of the bridging dinitrogen ligand in the Mo-N equivalent to N-Mo core.