Premium
Catalytic Disproportionation of Hydrazine Promoted by Biomimetic Diiron Complexes with Benzene‐1,2‐Dithiolate Bridge Modified by Different Substituents
Author(s) -
Sun Tie,
Xu Sunlin,
Yang Dawei,
Su Linan,
Wang Baomin,
Qu Jingping
Publication year - 2020
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.202000851
Subject(s) - disproportionation , chemistry , hydrazine (antidepressant) , catalysis , bimetallic strip , benzene , cyclic voltammetry , ligand (biochemistry) , catalytic cycle , medicinal chemistry , photochemistry , redox , ammonia , electrochemistry , yield (engineering) , inorganic chemistry , organic chemistry , biochemistry , materials science , receptor , electrode , chromatography , metallurgy
A series of thiolate‐bridged diiron nitrogenase mimics featuring benzene‐1,2‐dithiolate (bdt) ligand modified by different substituents were synthesized and characterized by X‐ray crystallography. Electrochemical studies by cyclic voltammetry demonstrate the redox potentials of these complexes depend on the electron‐withdrawing or electron‐donating nature of different substituents. Importantly, all these complexes can serve as catalysts for disproportionation of hydrazine to ammonia and dinitrogen, wherein the complex with the most negative reduction potential induced by strong electron‐donating NMe 2 group exhibits the best catalytic activity. This result bodes well for efficient catalyst design for N–N bond cleavage of hydrazine. In addition, a well‐defined diiron diazene complex can be independently synthesized and also catalyze the hydrazine disproportionation to ammonia. However, relatively low yield suggests this species may not be a key intermediate during the catalytic cycle, unlike the other reported bimetallic systems.