Activation of dinitrogen by group 6 metal complexes

• Published in: Russian chemical bulletin Vol. 72; no. 1; pp. 83 - 102
• Main Authors: Kireev, N. V., Filippov, O. A., Epstein, L. M., Shubina, E. S., Belkova, N. V.
• Format: Journal Article
• Language: English
• Published: New York Springer US 2023; Springer Nature B.V
• Subjects: Ammonia; Chemistry; Chemistry and Materials Science; Chemistry/Food Science; Coordination compounds; Electron transfer; Inorganic Chemistry; Nitrogen compounds; Organic Chemistry; Phosphines; Protonation; Reviews; Transition metals; group 6 metal complexes; proton transfer; reaction mechanism; nitrogen fixation
• ISSN: 1066-5285; 1573-9171
• DOI: 10.1007/s11172-023-3716-2

Fixation of atmospheric nitrogen and N 2 reduction to NH 3 under mild conditions form an important and, at the same time, challenging area of modern fundamental science. This review considers studies of the reactivity of dinitrogen complexes of group 6 metals (mainly molybdenum and tungsten) with relatively simple phosphine ligands, which made it possible to identify the main stages of N 2 reduction in the coordination sphere of a transition metal and factors affecting the reaction efficiency. The attention is focused on the studies of the protonation of the coordinated N 2 molecule, which is a key step in the catalytic cycle of nitrogen reduction, proceeding as alternating proton and electron transfer steps.