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A Terminal Imido Complex of an Iron–Sulfur Cluster
Author(s) -
Sridharan Arun,
Brown Alexandra C.,
Suess Daniel L. M.
Publication year - 2021
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202102603
Subject(s) - imes , chemistry , cluster (spacecraft) , iron–sulfur cluster , yield (engineering) , electron transfer , crystallography , bioinorganic chemistry , ferrous , sulfur , stereochemistry , medicinal chemistry , photochemistry , carbene , catalysis , organic chemistry , materials science , enzyme , computer science , metallurgy , programming language
We report the synthesis and characterization of the first terminal imido complex of an Fe–S cluster, (IMes) 3 Fe 4 S 4 =NDipp ( 2 ; IMes=1,3‐dimesitylimidazol‐2‐ylidene, Dipp=2,6‐diisopropylphenyl), which is generated by oxidative group transfer from DippN 3 to the all‐ferrous cluster (IMes) 3 Fe 4 S 4 (PPh 3 ). This two‐electron process is achieved by formal one‐electron oxidation of the imido‐bound Fe site and one‐electron oxidation of two IMes‐bound Fe sites. Structural, spectroscopic, and computational studies establish that the Fe–imido site is best described as a high‐spin Fe 3+ center, which is manifested in its long Fe−N(imido) distance of 1.763(2) Å. Cluster 2 abstracts hydrogen atoms from 1,4‐cyclohexadiene to yield the corresponding anilido complex, demonstrating competency for C−H activation.