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Activation of dinitrogen by group 6 metal complexes

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Abstract

Fixation of atmospheric nitrogen and N2 reduction to NH3 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 N2 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 N2 molecule, which is a key step in the catalytic cycle of nitrogen reduction, proceeding as alternating proton and electron transfer steps.

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Authors and Affiliations

  1. A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Build. 1, 28 ul. Vavilova, 119334, Moscow, Russian Federation

    N. V. Kireev, O. A. Filippov, L. M. Epstein, E. S. Shubina & N. V. Belkova

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  1. N. V. Kireev
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  2. O. A. Filippov
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  3. L. M. Epstein
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  4. E. S. Shubina
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  5. N. V. Belkova
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Corresponding author

Correspondence to N. V. Belkova.

Additional information

This study was performed within the framework of the State Assignment (No. 075-00697-22-00) of the Ministry of Science and Higher Education of the Russian Federation.

No human or animal subjects were used in this research.

The authors declare no competing interests.

Natalia Viktorovna Belkova, born in 1971, Doctor of Chemical Sciences, Professor of the Russian Academy of Sciences, Deputy Director for Science and Head of the Department of Organometallic Compounds of the A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, candidate for a Corresponding Member of the Russian Academy of Sciences in elections 2022, specialist in the physical organoelement chemistry, author of more than 320 scientific publications, including three book chapters and 114 papers in international peer-reviewed journals. The key scientific results of N. V. Belkova are concerned with catalytic systems based on transition metal complexes for reactions involving the activation of E-H bonds (E = C, N, O, B, metal) and conversion of small molecules. N. V. Belkova developed a methodology for integrated experimental and theoretical investigation of the mechanisms of stoichiometric and catalytic reactions involving transition metal complexes, in which the fundamentally important bond cleavage/formation steps are accomplished by cooperation of various functional sites, for example, hydrogenation of multiple bonds, dehydrocoupling of alcohols and silanes, H2 release from aminoboranes, and N2 reduction. N. V. Belkova is a member of the Editorial Boards of the journals Molecules and ChemistrySelect. N. V. Belkova supervised seven PhD students. She is a winner of the Prize of the European Academy for Young Scientists of C.I.S (1997); she received Acknowledgment from the Ministry of Science and Higher Education of the Russian Federation (2021).

Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, Vol. 72, No. 1, pp. 83–102, January, 2023.

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Kireev, N.V., Filippov, O.A., Epstein, L.M. et al. Activation of dinitrogen by group 6 metal complexes. Russ Chem Bull 72, 83–102 (2023). https://doi.org/10.1007/s11172-023-3716-2

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