Oxidation of nitroxyl radicals: electrochemical and computational studies

被引：47

作者：

Shibuya, Masatoshi ^{[2
]}

Pichierri, Fabio ^{[1
]}

Tomizawa, Masaki ^{[2
]}

Nagasawa, Shota ^{[2
]}

Suzuki, Iwao ^{[3
]}

Iwabuchi, Yoshiharu ^{[2
]}

机构：

[1] Tohoku Univ, G COE Lab, Dept Appl Chem, Grad Sch Engn, Sendai, Miyagi 9808579, Japan

[2] Tohoku Univ, Dept Organ Chem, Grad Sch Pharmaceut Sci, Sendai, Miyagi 9808578, Japan

[3] Takasaki Univ Hlth & Welf, Fac Pharm, Takasaki, Gunma 3700033, Japan

来源：

TETRAHEDRON LETTERS | 2012年 / 53卷 / 16期

基金：

日本学术振兴会;

关键词：

Nitroxyl radical; Cyclic voltammetry; DFT calculation; Organocatalysis; Redox potential; MOLECULAR-ORBITAL METHODS; AEROBIC OXIDATION; HIGHLY EFFICIENT; MEDIATED ELECTROOXIDATION; SECONDARY ALCOHOLS; TEMPO; ALDEHYDES; POTENTIALS; SALTS; ORGANOCATALYST;

D O I：

10.1016/j.tetlet.2012.02.033

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

We have developed azaadamantane-type nitroxyl radicals (AZADOs) and azabicyclo-type nitroxyl radicals (ABNOs) as highly active alcohol oxidation catalysts. Herein, the electrochemical properties of these nitroxyl radicals were investigated by measuring their formal potentials using cyclic voltammetry (CV). The redox potentials were rationalized with the aid of density functional theory (DFT) calculations. A good correlation between the experimental redox potential and the DFT-computed energy differences (Delta E) between nitroxyl radicals and oxoammonium species was obtained, which shows the effectiveness of DFT in predicting the redox potentials of nitroxyl radicals. Redox potential appears to be an important factor of catalytic activity. (C) 2012 Elsevier Ltd. All rights reserved.

引用

页码：2070 / 2073

页数：4

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