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Hydrazine Formation via Coupling of a Nickel(III)–NH 2 Radical
Author(s) -
Gu Nina X.,
Oyala Paul H.,
Peters Jonas C.
Publication year - 2021
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202013119
Subject(s) - hydrazine (antidepressant) , chemistry , catalysis , nickel , ammonia , amide , metal , adduct , redox , catalytic cycle , inorganic chemistry , medicinal chemistry , organic chemistry , chromatography
M(NH x ) intermediates involved in N−N bond formation are central to ammonia oxidation (AO) catalysis, an enabling technology to ultimately exploit ammonia (NH 3 ) as an alternative fuel source. While homocoupling of a terminal amide species (M‐NH 2 ) to form hydrazine (N 2 H 4 ) has been proposed, well‐defined examples are without precedent. Herein, we discuss the generation and electronic structure of a Ni III ‐NH 2 species that undergoes bimolecular coupling to generate a Ni II 2 (N 2 H 4 ) complex. This hydrazine adduct can be further oxidized to a structurally unusual Ni 2 (N 2 H 2 ) species; this releases N 2 in the presence of NH 3 , thus establishing a synthetic cycle for Ni‐mediated AO. Distribution of the redox load for H 2 N‐NH 2 formation via NH 2 coupling between two metal centers presents an attractive strategy for AO catalysis using Earth‐abundant, late first‐row metals.