KINETICS OF THERMAL GEOMETRICAL ISOMERIZATIONS OF 3 SETS OF ISOTOPICALLY LABELED CYCLOPROPANES FOLLOWED BY TUNABLE DIODE-LASER SPECTROSCOPY

被引：20

作者：

BALDWIN, JE ^{[1
]}

CIANCIOSI, SJ ^{[1
]}

GLENAR, DA ^{[1
]}

HOFFMAN, GJ ^{[1
]}

WU, IW ^{[1
]}

LEWIS, DK ^{[1
]}

机构：

[1] COLGATE UNIV,HAMILTON,NY 13346

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 1992年 / 114卷 / 24期

关键词：

D O I：

10.1021/ja00050a021

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

First-order rate constants for the approach to equilibrium through thermal geometrical isomerizations have been secured using tunable diode laser spectroscopy for three sets of isotopically labeled cyclopropanes. For the cis and trans 1,2-d2 cyclopropanes at 422.5-degrees-C, k(i)(d2) = (13.6 +/- 0.26) x 10(-5) s-1. For the syn and anti isomers of cyclopropane-1,2,3-d3 at 422.5-degrees-C, k(i)d3) = (15.5 +/- 0.47) x 10(-5) s-1. For the isomers of cyclopropane-1-C-13-1,2,3-d3 at 407.0-degrees-C, k(i)(C-13,d3) = (4.63 +/- 0.20) x 10(-5) s-1. These results are compared with independent determinations of two of these rate constants based on FTIR spectroscopy, and the relative advantages and limitations of the two spectroscopic techniques are compared.

引用

页码：9408 / 9414

页数：7

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