Oxidation of hydroquinones by a nonheme iron(IV)-oxo species

Kasi Nehru; Yukyeong Jang; Sunok Oh; Frédéric Dallemer; Wonwoo Nam; Jinheung Kim

doi:10.1016/j.ica.2007.12.027

Oxidation of hydroquinones by a nonheme iron(IV)-oxo species

Kasi Nehru, Yukyeong Jang, Sunok Oh, Frédéric Dallemer, Wonwoo Nam, Jinheung Kim

Department of Chemistry & Nanoscience

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

21 Scopus citations

Abstract

The reactivity of an isolated, well-characterized nonheme iron(IV)-oxo complex, [(TMC)Fe^IV{double bond, long}O]²⁺ (TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane), has been examined in the oxidation of hydroquinones. This complex has been shown to oxidize a series of hydroquinones, resulting in the production of the corresponding quinone products. Kinetic studies performed with substituted hydroquinones revealed a good correlation between reaction rates of the iron(IV)-oxo complex and the electron-donating ability of the substituents and the bond dissociation energy (BDE) of substrate O-H bonds. These results with a kinetic isotope effect (KIE) of 2.7 led us to propose a hydrogen-atom abstraction mechanism for the oxidation of hydroquinones by the nonheme iron(IV)-oxo species.

Original language	English
Pages (from-to)	2557-2561
Number of pages	5
Journal	Inorganica Chimica Acta
Volume	361
Issue number	8
DOIs	https://doi.org/10.1016/j.ica.2007.12.027
State	Published - 2 Jun 2008

Bibliographical note

Funding Information:
This work was supported by the SRC/ERC program of MOST/KOSEF (R11-2005-008-000-0 to J.K.), Seoul R& BD program (to J.K.), STAR program (2005–2007 to J.K. and F.D.), and the Ministry of Science and Technology of Korea through Creative Research Initiative Program (to W.N.).

Keywords

High-valent iron-oxo species
Hydrogen-atom abstraction
Hydroquinone
Nonheme iron enzymes
Oxidation

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title = "Oxidation of hydroquinones by a nonheme iron(IV)-oxo species",

abstract = "The reactivity of an isolated, well-characterized nonheme iron(IV)-oxo complex, [(TMC)FeIV{double bond, long}O]2+ (TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane), has been examined in the oxidation of hydroquinones. This complex has been shown to oxidize a series of hydroquinones, resulting in the production of the corresponding quinone products. Kinetic studies performed with substituted hydroquinones revealed a good correlation between reaction rates of the iron(IV)-oxo complex and the electron-donating ability of the substituents and the bond dissociation energy (BDE) of substrate O-H bonds. These results with a kinetic isotope effect (KIE) of 2.7 led us to propose a hydrogen-atom abstraction mechanism for the oxidation of hydroquinones by the nonheme iron(IV)-oxo species.",

keywords = "High-valent iron-oxo species, Hydrogen-atom abstraction, Hydroquinone, Nonheme iron enzymes, Oxidation",

author = "Kasi Nehru and Yukyeong Jang and Sunok Oh and Fr{\'e}d{\'e}ric Dallemer and Wonwoo Nam and Jinheung Kim",

note = "Funding Information: This work was supported by the SRC/ERC program of MOST/KOSEF (R11-2005-008-000-0 to J.K.), Seoul R& BD program (to J.K.), STAR program (2005–2007 to J.K. and F.D.), and the Ministry of Science and Technology of Korea through Creative Research Initiative Program (to W.N.). ",

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AU - Nehru, Kasi

AU - Jang, Yukyeong

AU - Oh, Sunok

AU - Dallemer, Frédéric

AU - Nam, Wonwoo

AU - Kim, Jinheung

N1 - Funding Information: This work was supported by the SRC/ERC program of MOST/KOSEF (R11-2005-008-000-0 to J.K.), Seoul R& BD program (to J.K.), STAR program (2005–2007 to J.K. and F.D.), and the Ministry of Science and Technology of Korea through Creative Research Initiative Program (to W.N.).

PY - 2008/6/2

Y1 - 2008/6/2

N2 - The reactivity of an isolated, well-characterized nonheme iron(IV)-oxo complex, [(TMC)FeIV{double bond, long}O]2+ (TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane), has been examined in the oxidation of hydroquinones. This complex has been shown to oxidize a series of hydroquinones, resulting in the production of the corresponding quinone products. Kinetic studies performed with substituted hydroquinones revealed a good correlation between reaction rates of the iron(IV)-oxo complex and the electron-donating ability of the substituents and the bond dissociation energy (BDE) of substrate O-H bonds. These results with a kinetic isotope effect (KIE) of 2.7 led us to propose a hydrogen-atom abstraction mechanism for the oxidation of hydroquinones by the nonheme iron(IV)-oxo species.

AB - The reactivity of an isolated, well-characterized nonheme iron(IV)-oxo complex, [(TMC)FeIV{double bond, long}O]2+ (TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane), has been examined in the oxidation of hydroquinones. This complex has been shown to oxidize a series of hydroquinones, resulting in the production of the corresponding quinone products. Kinetic studies performed with substituted hydroquinones revealed a good correlation between reaction rates of the iron(IV)-oxo complex and the electron-donating ability of the substituents and the bond dissociation energy (BDE) of substrate O-H bonds. These results with a kinetic isotope effect (KIE) of 2.7 led us to propose a hydrogen-atom abstraction mechanism for the oxidation of hydroquinones by the nonheme iron(IV)-oxo species.

KW - High-valent iron-oxo species

KW - Hydrogen-atom abstraction

KW - Hydroquinone

KW - Nonheme iron enzymes

KW - Oxidation

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Oxidation of hydroquinones by a nonheme iron(IV)-oxo species

Abstract

Bibliographical note

Keywords

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