Development of catalytic nitrogen fixation using transition metal complexes not relevant to nitrogenases

Abstract

Until 2015, well-defined transition metal complexes capable of catalyzing nitrogen reduction into ammonia or silylamines were limited to molybdenum and iron complexes, which are relevant to biological nitrogen fixation. In the last five years, other transition metal complexes not related to nitrogenases have been reported to exhibit catalytic activity toward nitrogen fixation under mild reaction conditions. This review article describes the historical background and recent advances on the conversion of dinitrogen into ammonia or silylamines catalyzed by transition metal complexes other than vanadium, molybdenum, and iron complexes. • Summary of the nitrogen fixation catalyzed by metal complexes except for Mo, Fe, V. • Ti, Re, Ru, Os, and Co complexes are active for catalytic NH 3 formation. • Ti, Cr, W, Mn, Re, Co, Rh, Ir, Ni, and U complexes catalyze dinitrogen silylation.