CeIV- and HClO4-Promoted Assembly of an Fe2IV(µ-O)2 Diamond Core from its Monomeric FeIV=O Precursor at Room Temperature.

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.