Catalytic nitrogen fixation via direct cleavage of nitrogen-nitrogen triple bond of molecular dinitrogen under ambient reaction conditions

Abstract

We have now found that molybdenumiodide complexes bearing a PNP-pincer ligand have a higher catalytic activity than the so far reported molybdenumdinitrogen 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 dimolybdenumiodide complex is a key point to promote direct cleavage of the nitrogennitrogen triple bond of the bridging dinitrogen ligand in the MoN τNMo core.