Open Access[2Fe–2S] Cluster Supported by Redox-Active o-Phenylenediamide Ligands and Its Application toward Dinitrogen Reduction
Author(s) -
Qiuming Liang,
Joshua DeMuth,
Aleksa Radović,
Nikki J. Wolford,
Michael L. Neidig,
Datong Song
Publication year - 2021
Publication title -
inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.348
H-Index - 233
eISSN - 1520-510X
pISSN - 0020-1669
DOI - 10.1021/acs.inorgchem.1c00683
Subject(s) - chemistry , redox , cluster (spacecraft) , catalysis , iron–sulfur cluster , cofactor , electron transfer , ligand (biochemistry) , sulfur , combinatorial chemistry , electrochemistry , amine gas treating , metal , photochemistry , inorganic chemistry , organic chemistry , enzyme , biochemistry , receptor , electrode , computer science , programming language
As prevalent cofactors in living organisms, iron-sulfur clusters participate in not only the electron-transfer processes but also the biosynthesis of other cofactors. Many synthetic iron-sulfur clusters have been used in model studies, aiming to mimic their biological functions and to gain mechanistic insight into the related biological systems. The smallest [2Fe-2S] clusters are typically used for one-electron processes because of their limited capacity. Our group is interested in functionalizing small iron-sulfur clusters with redox-active ligands to enhance their electron storage capacity, because such functionalized clusters can potentially mediate multielectron chemical transformations. Herein we report the synthesis, structural characterization, and catalytic activity of a diferric [2Fe-2S] cluster functionalized with two o -phenylenediamide ligands. The electrochemical and chemical reductions of such a cluster revealed rich redox chemistry. The functionalized diferric cluster can store up to four electrons reversibly, where the first two reduction events are ligand-based and the remainder metal-based. The diferric [2Fe-2S] cluster displays catalytic activity toward silylation of dinitrogen, affording up to 88 equiv of the amine product per iron center.