Aya Eizawa

Catalytic Reduction of Dinitrogen to Ammonia by Use of Molybdenum–Nitride Complexes Bearing a Tridentate Triphosphine as Catalysts

Newly designed and prepared molybdenum-nitride complexes bearing a mer-tridentate triphosphine as a ligand have been found to work as the most effective catalysts toward the catalytic reduction of dinitrogen to ammonia under ambient conditions, where up to 63 equiv of ammonia based on the Mo atom of the catalyst were produced.

Remarkable catalytic activity of dinitrogen-bridged dimolybdenum complexes bearing NHC-based PCP-pincer ligands toward nitrogen fixation

Intensive efforts for the transformation of dinitrogen using transition metal–dinitrogen complexes as catalysts under mild reaction conditions have been made. However, limited systems have succeeded in the catalytic formation of ammonia. Here we show that newly designed and prepared dinitrogen-bridged dimolybdenum complexes bearing N-heterocyclic carbene- and phosphine-based PCP-pincer ligands [{Mo(N2)2(PCP)}2(μ-N2)] (1) work as so far the most effective catalysts towards the formation of ammonia from dinitrogen under ambient reaction conditions, where up to 230 equiv. of ammonia are produced based on the catalyst. DFT calculations on 1 reveal that the PCP-pincer ligand serves as not only a strong σ-donor but also a π-acceptor. These electronic properties are responsible for a solid connection between the molybdenum centre and the pincer ligand, leading to the enhanced catalytic activity for nitrogen fixation.

Catalytic Reduction of Molecular Dinitrogen to Ammonia and Hydrazine Using Vanadium Complexes

Newly designed and prepared vanadium complexes bearing anionic pyrrole-based PNP-type pincer and aryloxy ligands were found to work as effective catalysts for the direct conversion of molecular dinitrogen into ammonia and hydrazine under mild reaction conditions. This is the first successful example of vanadium-catalyzed dinitrogen reduction under mild reaction conditions.

Catalytic Nitrogen Fixation Using Molybdenum–Dinitrogen Complexes as Catalysts

This chapter describes recent advances of molybdenum-catalyzed catalytic nitrogen fixation such as catalytic formation of silylamine and ammonia from dinitrogen under ambient reaction conditions. Hidai, Nishibayashi, Masuda, Mezailles, and their coworkers have achieved the molybdenum-catalyzed silylation and Schrock, Nishibayashi, and their coworkers have achieved the molybdenum-catalyzed formation of ammonia from nitrogen gas under ambient reaction conditions.

CCDC 1841926: Experimental Crystal Structure Determination

Related Article: Satoko Takaoka, Aya Eizawa, Shuhei Kusumoto, Kazunari Nakajima, Yoshiaki Nishibayashi, Kyoko Nozaki|2018|Organometallics|||doi:10.1021/acs.organomet.8b00377