Oxidation of nitroxyl radicals: Electrochemical and computational studies

Masatoshi Shibuya; Fabio Pichierri; Masaki Tomizawa; Shota Nagasawa; Iwao Suzuki; Yoshiharu Iwabuchi

doi:10.1016/j.tetlet.2012.02.033

Oxidation of nitroxyl radicals: Electrochemical and computational studies

Masatoshi Shibuya, Fabio Pichierri, Masaki Tomizawa, Shota Nagasawa, Iwao Suzuki, Yoshiharu Iwabuchi

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31 Citations (Scopus)

Abstract

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 (ΔE) 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.

Original language	English
Pages (from-to)	2070-2073
Number of pages	4
Journal	Tetrahedron Letters
Volume	53
Issue number	16
DOIs	https://doi.org/10.1016/j.tetlet.2012.02.033
Publication status	Published - 2012 Apr 18

Keywords

Cyclic voltammetry
DFT calculation
Nitroxyl radical
Organocatalysis
Redox potential

ASJC Scopus subject areas

Biochemistry
Drug Discovery
Organic Chemistry

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10.1016/j.tetlet.2012.02.033

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title = "Oxidation of nitroxyl radicals: Electrochemical and computational studies",

abstract = "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 (ΔE) 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.",

keywords = "Cyclic voltammetry, DFT calculation, Nitroxyl radical, Organocatalysis, Redox potential",

author = "Masatoshi Shibuya and Fabio Pichierri and Masaki Tomizawa and Shota Nagasawa and Iwao Suzuki and Yoshiharu Iwabuchi",

note = "Funding Information: This work was partly supported by a Grant-in-Aid for Scientific Research (B) (No. 21390001) (Y.I.) and by a Grant-in-Aid for Young Scientists (A) (No. 23689001) (M.S.) from the Japan Society for the Promotion of Science (JSPS). F.P. thanks the Global COE Program of Tohoku University for financial support. ",

year = "2012",

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day = "18",

doi = "10.1016/j.tetlet.2012.02.033",

language = "English",

volume = "53",

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T2 - Electrochemical and computational studies

AU - Shibuya, Masatoshi

AU - Pichierri, Fabio

AU - Tomizawa, Masaki

AU - Nagasawa, Shota

AU - Suzuki, Iwao

AU - Iwabuchi, Yoshiharu

N1 - Funding Information: This work was partly supported by a Grant-in-Aid for Scientific Research (B) (No. 21390001) (Y.I.) and by a Grant-in-Aid for Young Scientists (A) (No. 23689001) (M.S.) from the Japan Society for the Promotion of Science (JSPS). F.P. thanks the Global COE Program of Tohoku University for financial support.

PY - 2012/4/18

Y1 - 2012/4/18

N2 - 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 (ΔE) 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.

AB - 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 (ΔE) 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.

KW - Cyclic voltammetry

KW - DFT calculation

KW - Nitroxyl radical

KW - Organocatalysis

KW - Redox potential

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DO - 10.1016/j.tetlet.2012.02.033

M3 - Article

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JO - Tetrahedron Letters

JF - Tetrahedron Letters

SN - 0040-4039

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Oxidation of nitroxyl radicals: Electrochemical and computational studies

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Keywords

ASJC Scopus subject areas

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