Catalytic Reduction of Dinitrogen into Ammonia and Hydrazine by Using Chromium Complexes Bearing PCP-Type Pincer Ligands

Yuya Ashida; Akihito Egi; Kazuya Arashiba; Hiromasa Tanaka; Taichi Mitsumoto; Shogo Kuriyama; Kazunari Yoshizawa; Yoshiaki Nishibayashi

doi:10.1002/chem.202200557

Catalytic Reduction of Dinitrogen into Ammonia and Hydrazine by Using Chromium Complexes Bearing PCP-Type Pincer Ligands

Chemistry. 2022 May 2;28(25):e202200557. doi: 10.1002/chem.202200557. Epub 2022 Mar 28.

Authors

Yuya Ashida¹, Akihito Egi², Kazuya Arashiba¹, Hiromasa Tanaka³, Taichi Mitsumoto¹, Shogo Kuriyama¹, Kazunari Yoshizawa², Yoshiaki Nishibayashi¹

Affiliations

¹ Department of Applied Chemistry, School of Engineering, The University of Tokyo, Hongo, Bunkyo-ku, Tokyo, 113-8656, Japan.
² Institute for Materials Chemistry and Engineering, Kyushu University, Nishi-ku, Fukuoka, Japan.
³ School of Liberal Arts and Sciences, Daido University, Minami-ku, Nagoya, Japan.

PMID: 35199891
DOI: 10.1002/chem.202200557

Abstract

A series of chromium-halide, -nitride, and -dinitrogen complexes bearing carbene- and phosphine-based PCP-type pincer ligands has been newly prepared, and some of them are found to work as effective catalysts to reduce dinitrogen under atmospheric pressure, whereby up to 11.60 equiv. of ammonia and 2.52 equiv. of hydrazine (16.6 equiv. of fixed N atom) are produced based on the chromium atom. To the best of our knowledge, this is the first successful example of chromium-catalyzed conversion of dinitrogen to ammonia and hydrazine under mild reaction conditions.

Keywords: ammonia; chromium; homogeneous catalysis; nitrogen fixation; pincer ligand.