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

Apparao Draksharapu, Shuangning Xu, Lawrence Que

Research output: Contribution to journalArticlepeer-review


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*)FeII (1) (TPA*=tris(3,5-dimethyl-4-methoxypyridyl-2-methyl)amine) in CH3CN with 4 equiv CAN and 200 equiv HClO4 at 20 °C to form a complex with an [FeIV2(μ-O)2]4+ core. CAN and HClO4 play essential roles in this unprecedented transformation, in which the comproportionation of FeIII-O-CeIV and FeIV=O/Ce4+ species is proposed to be involved in the assembly of the [FeIV2(μ-O)2]4+ core.

Original languageEnglish (US)
Pages (from-to)22484-22488
Number of pages5
JournalAngewandte Chemie - International Edition
Issue number50
StatePublished - Dec 7 2020

Bibliographical note

Funding Information:
The authors gratefully acknowledge grants from the U. S. National Institutes of Health (R01 GM‐38767 and R35 GM‐131721 to L.Q.) in support of this work. XAS data were collected at the Stanford Synchrotron Radiation Lightsource, which is supported by the U.S. DOE under Contract No. DE‐AC02‐76SF00515. Use of Beamline 9‐3 is supported by the DOE Office of Biological and Environmental Research and the National Institutes of Health, National Institute of General Medical Sciences (including P41GM103393).


  • CAN
  • Fe-O-Ce complex
  • diamond core
  • diiron(IV)
  • oxoiron(IV) complex

PubMed: MeSH publication types

  • Journal Article
  • Research Support, N.I.H., Extramural

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