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

doi:10.1002/anie.202010027

Ce^IV- and HClO₄-Promoted Assembly of an Fe₂^IV(μ-O)₂ Diamond Core from its Monomeric Fe^IV=O Precursor at Room Temperature

Apparao Draksharapu, Shuangning Xu, Lawrence Que

Chemistry (Twin Cities)

Research output: Contribution to journal › Article › peer-review

4 Scopus citations

Abstract

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 CH₃CN with 4 equiv CAN and 200 equiv HClO₄ at 20 °C to form a complex with an [Fe^IV₂(μ-O)₂]⁴⁺ core. CAN and HClO₄ play essential roles in this unprecedented transformation, in which the comproportionation of Fe^III-O-Ce^IV and Fe^IV=O/Ce⁴⁺ species is proposed to be involved in the assembly of the [Fe^IV₂(μ-O)₂]⁴⁺ core.

Original language	English (US)
Pages (from-to)	22484-22488
Number of pages	5
Journal	Angewandte Chemie - International Edition
Volume	59
Issue number	50
DOIs	https://doi.org/10.1002/anie.202010027
State	Published - 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).

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).

Publisher Copyright:
© 2020 Wiley-VCH GmbH

Keywords

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

Publisher link

10.1002/anie.202010027

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@article{27694288e87749029a531bc55dabf7dc,

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

abstract = "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.",

keywords = "CAN, Fe-O-Ce complex, diamond core, diiron(IV), oxoiron(IV) complex",

author = "Apparao Draksharapu and Shuangning Xu and Lawrence Que",

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). 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). Publisher Copyright: {\textcopyright} 2020 Wiley-VCH GmbH",

year = "2020",

month = dec,

day = "7",

doi = "10.1002/anie.202010027",

language = "English (US)",

volume = "59",

pages = "22484--22488",

journal = "Angewandte Chemie - International Edition",

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T1 - CeIV- and HClO4-Promoted Assembly of an Fe2IV(μ-O)2 Diamond Core from its Monomeric FeIV=O Precursor at Room Temperature

AU - Draksharapu, Apparao

AU - Xu, Shuangning

AU - Que, Lawrence

N1 - 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). 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). Publisher Copyright: © 2020 Wiley-VCH GmbH

PY - 2020/12/7

Y1 - 2020/12/7

N2 - 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.

AB - 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.

KW - CAN

KW - Fe-O-Ce complex

KW - diamond core

KW - diiron(IV)

KW - oxoiron(IV) complex

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