Structural isomerization of cyclopropane: a new mechanism through propylidene

被引：24

作者：

Bettinger, HF

Rienstra-Kiracofe, JC

Hoffman, BC

Schaefer, HF

Baldwin, JE

Schleyer, PV

机构：

[1] Univ Georgia, Ctr Computat Quantum Chem, Athens, GA 30602 USA

[2] Syracuse Univ, Dept Chem, Syracuse, NY 13244 USA

来源：

CHEMICAL COMMUNICATIONS | 1999年 / 16期

关键词：

D O I：

10.1039/a901886g

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Ab initio coupled cluster methods indicate that the isomerization of cyclopropane to propene (E-a = 64-66 kcal mol(-1) experimentally) might involve two differentmechanisms: the barrier for the newly proposed pathway through propylidene is only slightly higher (Delta E double dagger = 66.6 kcal mol(-1)) than that of the traditional trimethylene route (Delta E double dagger = 64.2 kcal mol(-1)).

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收藏

页码：1515 / 1516

页数：2

相关论文

共 38 条

[1]

ALMLOF J, ACES 2 IS PROGRAM PR

[2] THERMAL STEREOMUTATIONS OF CYCLOPROPANE AND OF ISOTOPICALLY LABELED CYCLOPROPANES ASSESSED THROUGH AB-INITIO COMPUTATIONAL METHODS AND KINETIC ISOTOPE EFFECT CALCULATIONS [J].

BALDWIN, JE ;

YAMAGUCHI, Y ;

SCHAEFER, HF .

JOURNAL OF PHYSICAL CHEMISTRY, 1994, 98 (31) :7513-7522

[3]

BALDWIN JE, 1995, CHEM CYCLOPROPYL GRO, V2, pCH9

[4] REACTION OF CYCLOPROPANE WITH IODINE AND SOME OBSERVATIONS ON ISOMERIZATION OF CYCLOPROPANE [J].

BENSON, SW .

JOURNAL OF CHEMICAL PHYSICS, 1961, 34 (02) :521-&

[5] CONFIRMATION OF THE H-BRIDGED STRUCTURE OF THE 2-BUTYL CATION BY COMPARISON OF EXPERIMENTAL AND ABINITIO IR FREQUENCIES [J].

BUZEK, P ;

SCHLEYER, PV ;

SIEBER, S ;

KOCH, W ;

CARNEIRO, JWD ;

VANCIK, H ;

SUNKO, DE .

JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1991, (10) :671-674

[6]

CARNEIRO JWM, 1990, J AM CHEM SOC, V12, P4064

[7] Kinetics of the thermal isomerization of cyclopropane [J].

Chambers, TS ;

Kistiakowsky, GB .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1934, 56 :399-405

[8] Direct dynamics study of the stereomutation of cyclopropane [J].

Doubleday, C ;

Bolton, K ;

Hase, WL .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1997, 119 (22) :5251-5252

[9] Direct dynamics quasiclassical trajectory study of the thermal stereomutations of cyclopropane [J].

Doubleday, C ;

Bolton, K ;

Hase, WL .

JOURNAL OF PHYSICAL CHEMISTRY A, 1998, 102 (21) :3648-3658

[10] Lifetime of trimethylene calculated by variational unimolecular rate theory [J].

Doubleday, C .

JOURNAL OF PHYSICAL CHEMISTRY, 1996, 100 (09) :3520-3526

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