The Energetics of Halogenated Ethylenes (Ethynes) and 1,3-Butadienes (Butadiynes): A Computational and Conceptual Study of Substituent Effects and "Dimerization"

被引：0

作者：

Deakyne, Carol A. ^{[1
]}

Warfel, Lawrence H. ^{[1
]}

Thomas, Haunani M. ^{[1
]}

Nauduri, Dhananjaya ^{[2
]}

Ajibowo, Toyosi Esther A. ^{[3
]}

Carbonaro, Nicole J. ^{[3
]}

Simpson, Alec G. ^{[3
]}

Liebman, Joel F. ^{[3
]}

机构：

[1] Univ Missouri, Dept Chem, Columbia, MO 65211 USA

[2] Univ Texas Med Branch, Dept Pathol & Mol Toxicol, Galveston, TX 77555 USA

[3] Univ Maryland Baltimore Cty, Dept Chem & Biochem, Baltimore, MD 21250 USA

来源：

CROATICA CHEMICA ACTA | 2009年 / 82卷 / 01期

关键词：

dienes; diynes; halogenated compounds; resonance (conjugation) energy; isodesmic reactions; ab initio calculations; CORRELATED MOLECULAR CALCULATIONS; GAUSSIAN-BASIS SETS; 3; ISOMERS; ATOMS ALUMINUM; THERMOCHEMISTRY; COMPLEXES; ENERGIES;

D O I：

暂无

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The energetics of ethylenes and 1,3-butadienes may be interrelated by the reaction: RHC=CH2 + H2C=CHR' -> RHC=CH-CH=CHR' + H-2. Shown earlier to be nearly enthalpically thermoneutral for a variety of hydrocarbon cases, we are now interested in the related energetics of halogenated alkenes and alkynes. Using quantum chemical calculations, we have studied this as recast as the isodesmic reactions: 2(H2C=CHX) + H2C=CH-CH=CH2 -> p,q-di-X-1,3-butadiene + 2H(2)C=CH2 2(HC CX) + HC C-C CH -> di-X-butadiyne + 2HC CH. Here p,q-= 1,3-; 1,4- and 2,3- with X = F, Cl, Br, and 1. The halogen and location-dependent deviations from near enthalpic thermoneutrality are discussed.

引用

页码：165 / 172

页数：8