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Ce IV ‐ and HClO 4 ‐Promoted Assembly of an Fe 2 IV (μ‐O) 2 Diamond Core from its Monomeric Fe IV =O Precursor at Room Temperature
Author(s) -
Draksharapu Apparao,
Xu Shuangning,
Que Lawrence
Publication year - 2020
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202010027
Subject(s) - comproportionation , chemistry , methane monooxygenase , monomer , medicinal chemistry , amine gas treating , tris , group 2 organometallic chemistry , bond cleavage , phosphine , inorganic chemistry , stereochemistry , methane , molecule , catalysis , organic chemistry , electrochemistry , polymer , biochemistry , electrode
Diiron(IV)‐oxo species are proposed to effect the cleavage of strong C−H bonds by nonheme diiron enzymes such as soluble methane monooxygenase (sMMO) and fatty acid desaturases. However, synthetic mimics of such diiron(IV) oxidants are rare. Herein we report the reaction of (TPA*)Fe II ( 1 ) (TPA*=tris(3,5‐dimethyl‐4‐methoxypyridyl‐2‐methyl)amine) in CH 3 CN with 4 equiv CAN and 200 equiv HClO 4 at 20 °C to form a complex with an [Fe IV 2 (μ‐O) 2 ] 4+ core. CAN and HClO 4 play essential roles in this unprecedented transformation, in which the comproportionation of Fe III ‐O‐Ce IV and Fe IV =O/Ce 4+ species is proposed to be involved in the assembly of the [Fe IV 2 (μ‐O) 2 ] 4+ core.