Fragmentation of aryl halide π anion radicals.: Bending of the cleaving bond and activation vs driving force relationships

被引：155

作者：

Costentin, C ^{[1
]}

Robert, M ^{[1
]}

Savéant, JM ^{[1
]}

机构：

[1] Univ Paris 07, CNRS, UMR 7591, Electrochim Mol Lab, F-75251 Paris 05, France

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2004年 / 126卷 / 49期

关键词：

D O I：

10.1021/ja045989u

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Recent rate data for very fast cleaving of aryl chloride and bromide anion radicals may be accommodated satisfactorily within rate constant versus ArX/ArX.- standard potential existing correlations provided the standard potential is determined experimentally. Cyclic voltammetry is used for this purpose, taking careful account of the electron transfer/fragmentation reaction mixed character of the kinetics. The ensuing activation/driving force relationships allow the determination of the intrinsic barriers, the magnitude of which are discussed in the framework of a new Morse curve model that includes and emphasizes the role of bond bending.

引用

页码：16051 / 16057

页数：7

共 56 条

[1] ELECTROCHEMICALLY INDUCED REACTIONS - KINETICS OF THE COMPETITION WITH HOMOGENEOUS ELECTRON-TRANSFER IN NON-CATALYTIC SYSTEMS - APPLICATION TO THE SUBSTITUTION OF 4-BROMOBENZOPHENONE BY CYANIDE IONS IN LIQUID-AMMONIA [J].

AMATORE, C ;

SAVEANT, JM ;

COMBELLAS, C ;

ROBVEILLE, S ;

THIEBAULT, A .

JOURNAL OF ELECTROANALYTICAL CHEMISTRY, 1985, 184 (01) :25-40

[2]

AMATORE C, 1977, J ELECTROANAL CHEM, V85, P27, DOI 10.1016/S0022-0728(77)80150-2

[3] ELECTROCHEMICALLY CATALYZED AROMATIC NUCLEOPHILIC-SUBSTITUTION - REACTIVITY OF CYANIDE IONS TOWARD ARYL RADICALS IN LIQUID-AMMONIA [J].

AMATORE, C ;

COMBELLAS, C ;

ROBVEILLE, S ;

SAVEANT, JM ;

THIEBAULT, A .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1986, 108 (16) :4754-4760

[4] ELECTROCHEMICALLY INDUCED SRN1 AROMATIC NUCLEOPHILIC-SUBSTITUTION - ABSOLUTE REACTIVITIES OF PHENYL DERIVATIVES IN LIQUID-AMMONIA [J].

AMATORE, C ;

COMBELLAS, C ;

PINSON, J ;

OTURAN, MA ;

ROBVEILLE, S ;

SAVEANT, JM ;

THIEBAULT, A .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1985, 107 (17) :4846-4853

[5] 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

[6] The standard redox potential of the phenyl radical/anion couple [J].

Andrieux, CP ;

Pinson, J .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2003, 125 (48) :14801-14806

[7] FAST CHEMICAL STEPS COUPLED WITH OUTER-SPHERE ELECTRON TRANSFERS - APPLICATION OF FAST SCAN VOLTAMMETRY AT ULTRAMICROELECTRODES TO THE CLEAVAGE OF AROMATIC HALIDE ANION RADICALS IN THE MICROSECOND LIFETIME RANGE [J].

ANDRIEUX, CP ;

HAPIOT, P ;

SAVEANT, JM .

JOURNAL OF PHYSICAL CHEMISTRY, 1988, 92 (21) :5987-5992

[8] HETEROGENEOUS AND HOMOGENEOUS ELECTRON TRANSFERS TO AROMATIC HALIDES - ELECTROCHEMICAL REDOX CATALYSIS STUDY IN THE HALOBENZENE AND HALOPYRIDINE SERIES [J].

ANDRIEUX, CP ;

BLOCMAN, C ;

DUMASBOUCHIAT, JM ;

SAVEANT, JM .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1979, 101 (13) :3431-3441

[9] Concerted and stepwise dissociative electron transfers. Oxidability of the leaving group and strength of the breaking bond as mechanism and reactivity governing factors illustrated by the electrochemical reduction of alpha-substituted acetophenones [J].

Andrieux, CP ;

Saveant, JM ;

Tallec, A ;

Tardivel, R ;

Tardy, C .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1997, 119 (10) :2420-2429

[10] 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

← 1 2 3 4 5 6 →