Small Reorganization Energy for Ligand-Centered Electron-Transfer Reduction of Compound I to Compound II in a Heme Model Study

被引：14

作者：

Fukui, Nami ^{[1
]}

Li, Xiao-Xi ^{[2
]}

Nam, Wonwoo ^{[2
]}

Fukuzumi, Shunichi ^{[2
,3
]}

Fujii, Hiroshi ^{[1
]}

机构：

[1] Nara Womens Univ, Grad Sch Humanities & Sci, Dept Chem, Nara 6508506, Japan

[2] Ewha Womans Univ, Dept Chem & Nano Sci, Seoul 03760, South Korea

[3] Meijo Univ, Japan Sci & Technol Agcy, SENTAN, Fac Sci & Engn, Nagoya, Aichi 4680073, Japan

来源：

INORGANIC CHEMISTRY | 2019年 / 58卷 / 13期

关键词：

COMPLEXES; PARTICIPATION; SULFOXIDATION; REACTIVITY; ACTIVATION; MECHANISMS; ENZYMES;

D O I：

10.1021/acs.inorgchem.9b01051

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The electron-transfer (ET) processes from electron-donor substrates to oxoiron(IV) porphyrin pi-cation-radical species (Cpd I) are key steps in their oxygenation reactions. Here, we have evaluated the rate constants of the outer-sphere ET reduction of Cpd I model complexes of meso-tetramesitylporphyrin (1) and 2,7,12,17-tetramesity1-3,8,13,18-tetramethylporphyrin (2) in light of the Marcus theory of ET to determine the ET reorganization energies (lambda). The lambda values of the ligand-centered ET reduction of Cpd I model complexes are much smaller than those of the metal-centered ET reduction of various oxoiron(IV) complexes. Moreover, the lambda value of 1 is larger than that of 2, resulting from the difference in the nature of the a(1u)/a(2u) porphyrin pi-cation radical orbitals.

引用

页码：8263 / 8266

页数：4

共 22 条

[1] Participation of Electron Transfer Process in Rate-Limiting Step of Aromatic Hydroxylation Reactions by Compound I Models of Heme Enzymes [J].

Asaka, Maaya ;

Fujii, Hiroshi .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2016, 138 (26) :8048-8051

[2] pH and driving force dependence of intramolecular oxyferryl heme reduction in myoglobin [J].

Fenwick, CW ;

English, AM ;

Wishart, JF .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1997, 119 (20) :4758-4764

[3] EFFECTS OF THE ELECTRON-WITHDRAWING POWER OF SUBSTITUENTS ON THE ELECTRONIC-STRUCTURE AND REACTIVITY IN OXOIRON(IV) PORPHYRIN PI-CATION RADICAL COMPLEXES [J].

FUJII, H .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1993, 115 (11) :4641-4648

[4]

Fujii H, 2016, RSC METALLOBIO SER, V4, P183

[5] Electron-transfer kinetics for generation of organoiron(IV) porphyrins and the iron(IV) porphyrin π radical cations [J].

Fukuzumi, S ;

Nakanishi, I ;

Tanaka, K ;

Suenobu, T ;

Tabard, A ;

Guilard, R ;

Van Caemelbecke, E ;

Kadish, KM .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1999, 121 (04) :785-790

[6] Electron-transfer properties of high-valent metal-oxo complexes [J].

Fukuzumi, Shunichi .

COORDINATION CHEMISTRY REVIEWS, 2013, 257 (9-10) :1564-1575

[7] Electron- and Hydride-Transfer Reactivity of an Isolable Manganese(V)-Oxo Complex [J].

Fukuzumi, Shunichi ;

Kotani, Hiroaki ;

Prokop, Katharine A. ;

Goldberg, David P. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2011, 133 (06) :1859-1869

[8] Mechanistic Insights into Hydride-Transfer and Electron-Transfer Reactions by a Manganese(IV)-Oxo Porphyrin Complex [J].

Fukuzumi, Shunichi ;

Fujioka, Naofumi ;

Kotani, Hiroaki ;

Ohkubo, Kei ;

Lee, Yong-Min ;

Nam, Wonwoo .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2009, 131 (47) :17127-17134

[9] Mechanisms of N-demethylations catalyzed by high-valent species of heme enzymes: Novel use of isotope effects and direct observation of intermediates [J].

Goto, Y ;

Watanabe, Y ;

Fukuzumi, S ;

Jones, JP ;

Dinnocenzo, JP .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1998, 120 (41) :10762-10763

[10] Mechanisms of sulfoxidation catalyzed by high-valent intermediates of heme enzymes: Electron-transfer vs oxygen-transfer mechanism [J].

Goto, Y ;

Matsui, T ;

Ozaki, S ;

Watanabe, Y ;

Fukuzumi, S .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1999, 121 (41) :9497-9502

← 1 2 3 →