THEORETICAL INVESTIGATION OF THE ORIGIN OF SECONDARY ALPHA-DEUTERIUM KINETIC ISOTOPE EFFECTS

被引：45

作者：

BARNES, JA ^{[1
]}

WILLIAMS, IH ^{[1
]}

机构：

[1] UNIV BATH,SCH CHEM,BATH BA2 7AY,AVON,ENGLAND

来源：

JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS | 1993年 / 16期

关键词：

D O I：

10.1039/c39930001286

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Although the secondary alpha-deuterium kinetic isotope effect upon the degenerate S(N)2 reaction of chloromethane with chloride anion arises from changes in alpha-CH stretching force constants, alpha-substitution by methyl and/or methoxygroups shows this inverse inductive contribution to be approximately constant and reveals that the trend in the isotope effect (calculated by semiempirical molecular orbital theory) is determined by changes in bending force constants, in accord with the conventional view.

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页码：1286 / 1287

页数：2

相关论文

共 15 条

[1] BIMOLECULAR NUCLEOPHILIC-SUBSTITUTION ON AN ACETAL [J].

CRAZE, GA ;

KIRBY, AJ ;

OSBORNE, R .

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 1978, (04) :357-369

[2] THE DEVELOPMENT AND USE OF QUANTUM-MECHANICAL MOLECULAR-MODELS .76. AM1 - A NEW GENERAL-PURPOSE QUANTUM-MECHANICAL MOLECULAR-MODEL [J].

DEWAR, MJS ;

ZOEBISCH, EG ;

HEALY, EF ;

STEWART, JJP .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1985, 107 (13) :3902-3909

[3] DEUTERIUM-ISOTOPE EFFECTS IN GAS-PHASE REACTIONS OF ALKYL-HALIDES - DISTINGUISHING E2 AND SN2 PATHWAYS [J].

GRONERT, S ;

DEPUY, CH ;

BIERBAUM, VM .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1991, 113 (10) :4009-4010

[4] MECHANISM OF REACTIONS OF N-(METHOXYMETHYL)-N,N-DIMETHYLANILINIUM IONS WITH NUCLEOPHILIC-REAGENTS [J].

KNIER, BL ;

JENCKS, WP .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1980, 102 (22) :6789-6798

[5] SOME DEUTERIUM KINETIC ISOTOPE EFFECTS .2. ALPHA-DEUTERIUM EFFECTS IN THE WATER SOLVOLYSIS OF SOME ALKYL COMPOUNDS [J].

LEFFEK, KT ;

LLEWELLYN, JA ;

ROBERTSON, RE .

CANADIAN JOURNAL OF CHEMISTRY-REVUE CANADIENNE DE CHIMIE, 1960, 38 (09) :1505-1510

[6]

Leffler JE., 1989, RATES EQUILIBRIA ORG

[7]

Melander L, 1980, REACTION RATES ISOTO

[8]

Shiner V. J., 1970, ISOTOPE EFFECTS CHEM

[9] KINETIC ISOTOPE EFFECTS IN THE ACETOLYSES OF DEUTERATED CYCLOPENTYL TOSYLATES [J].

STREITWIESER, A ;

JAGOW, RH ;

FAHEY, RC ;

SUZUKI, S .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1958, 80 (09) :2326-2332

[10] ON THE REPRESENTATION OF FORCE-FIELDS FOR CHEMICALLY REACTING SYSTEMS [J].

WILLIAMS, IH .

CHEMICAL PHYSICS LETTERS, 1982, 88 (05) :462-466