TY - JOUR
T1 - Oxidation of hydroquinones by a nonheme iron(IV)-oxo species
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
UR - http://www.scopus.com/inward/record.url?scp=43949118424&partnerID=8YFLogxK
U2 - 10.1016/j.ica.2007.12.027
DO - 10.1016/j.ica.2007.12.027
M3 - Article
AN - SCOPUS:43949118424
SN - 0020-1693
VL - 361
SP - 2557
EP - 2561
JO - Inorganica Chimica Acta
JF - Inorganica Chimica Acta
IS - 8
ER -