HOMOGENEOUS REDOX CATALYSIS - APPLICATION TO THE KINETIC CHARACTERIZATION OF INTERMEDIATES UNDERGOING FAST BIMOLECULAR DECAY APPROACHING THE DIFFUSION LIMIT

被引：12

作者：

ANDRIEUX, CP

ANNE, A

MOIROUX, J

SAVEANT, JM

机构：

[1] Laboratoire d'Electrochimie Moléculaire, Université de Paris 7, URA 437, 75251 Paris Cedex 05

来源：

JOURNAL OF ELECTROANALYTICAL CHEMISTRY | 1991年 / 307卷 / 1-2期

关键词：

D O I：

10.1016/0022-0728(91)85536-X

中图分类号：

O65 [分析化学];

学科分类号：

070302 ; 081704 ;

摘要：

The homogeneous redox catalysis method for determining the rate constants of fast reactions after the electron transfer step, which up to now has been used for monomolecular or pseudo-first order reactions, is extended to bimolecular reactions. Rate constants approaching the diffusion limit can be readily determined using the procedures proposed. The practical application of this method has been tested successfully using as an example the oxidation of N-benzyldihydronicotinamide, a synthetic analogue of NADH, and the deprotonation of its cation radical by benzylamine in acetonitrile.

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页码：17 / 28

页数：12

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共 28 条

[1] NUCLEOPHILE AND ARYL RADICAL REACTIVITY IN SRN1 AROMATIC NUCLEOPHILIC-SUBSTITUTION REACTIONS - ABSOLUTE AND RELATIVE ELECTROCHEMICAL DETERMINATION [J].

AMATORE, C ;

OTURAN, MA ;

PINSON, J ;

SAVEANT, JM ;

THIEBAULT, A .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1985, 107 (12) :3451-3459

[2] ELECTRON-TRANSFER-INDUCED REACTIONS - A NOVEL-APPROACH BASED ON ELECTROCHEMICAL REDOX CATALYSIS - APPLICATION TO AROMATIC NUCLEOPHILIC SUBSTITUTIONS [J].

AMATORE, C ;

OTURAN, MA ;

PINSON, J ;

SAVEANT, JM ;

THIEBAULT, A .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1984, 106 (21) :6318-6321

[3] A STUDY OF THE PRIMARY ACID REACTION ON MODEL COMPOUNDS OF REDUCED DIPHOSPHOPYRIDINE NUCLEOTIDE [J].

ANDERSON, AG ;

BERKELHAMMER, G .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1958, 80 (04) :992-999

[4] HOMOGENEOUS REDOX CATALYSIS OF ELECTROCHEMICAL REACTIONS .5. CYCLIC VOLTAMMETRY [J].

ANDRIEUX, CP ;

BLOCMAN, C ;

DUMASBOUCHIAT, JM ;

MHALLA, F ;

SAVEANT, JM .

JOURNAL OF ELECTROANALYTICAL CHEMISTRY, 1980, 113 (01) :19-40

[5] PRECEDING CHEMICAL-REACTION MECHANISMS IN HOMOGENEOUS ELECTRON-TRANSFER REACTIONS - MEDIATED ELECTROCHEMICAL REDUCTION OF HIGHLY REACTIVE BENZYLIC HALIDES [J].

ANDRIEUX, CP ;

MERZ, A ;

SAVEANT, JM ;

TOMAHOGH, R .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1984, 106 (07) :1957-1962

[6] DISSOCIATIVE ELECTRON-TRANSFER - AUTO-CATALYSIS AND KINETIC CHARACTERISTICS OF THE ELECTROCHEMICAL REDUCTIVE CLEAVAGE OF THE CARBON-HALOGEN BOND IN ALKYL-HALIDES GIVING RISE TO STABLE RADICALS AND CARBANIONS [J].

ANDRIEUX, CP ;

MERZ, A ;

SAVEANT, JM .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1985, 107 (21) :6097-6103

[7] FAST KINETICS BY MEANS OF DIRECT AND INDIRECT ELECTROCHEMICAL TECHNIQUES [J].

ANDRIEUX, CP ;

HAPIOT, P ;

SAVEANT, JM .

CHEMICAL REVIEWS, 1990, 90 (05) :723-738

[8] DETERMINATION OF THE LIFETIMES OF UNSTABLE ION RADICALS BY HOMOGENEOUS REDOX CATALYSIS OF ELECTROCHEMICAL REACTIONS - APPLICATION TO THE REDUCTION OF AROMATIC HALIDES [J].

ANDRIEUX, CP ;

BLOCMAN, C ;

DUMASBOUCHIAT, JM ;

MHALLA, F ;

SAVEANT, JM .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1980, 102 (11) :3806-3813

[9]

ANDRIEUX CP, 1986, TECHNIQUES CHEM 2, V6, P305

[10] OXIDATION OF 10-METHYLACRIDAN, A SYNTHETIC ANALOG OF NADH, AND DEPROTONATION OF ITS CATION RADICAL - CONVERGENT APPLICATION OF LASER FLASH-PHOTOLYSIS AND DIRECT AND REDOX CATALYZED ELECTROCHEMISTRY TO THE KINETICS OF DEPROTONATION OF THE CATION RADICAL [J].

ANNE, A ;

HAPIOT, P ;

MOIROUX, J ;

NETA, P ;

SAVEANT, JM .

JOURNAL OF PHYSICAL CHEMISTRY, 1991, 95 (06) :2370-2377