Chiral discrimination and isomerization processes in monomers, dimers and trimers of sulfoxides and thioperoxides

被引：14

作者：

Alkorta, I ^{[1
]}

Picazo, O ^{[1
]}

Elguero, J ^{[1
]}

机构：

[1] CSIC, Inst Quim Med, E-28006 Madrid, Spain

来源：

TETRAHEDRON-ASYMMETRY | 2004年 / 15卷 / 09期

关键词：

D O I：

10.1016/j.tetasy.2004.03.021

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The chiral discrimination in cyclic dieters and trimers of mono-substituted sulfoxides and thioperoxides has been studied by means of DFT (B3LYP/6-31+G**) and ab initio (MP2/6-311+G**) calculations. In addition, the inter- and intramolecular proton transfer processes that interconvert these two classes of compounds have been considered for the isolated molecules and clusters. The thioperoxide clusters are more stable than the corresponding sulfoxides even though the strongest hydrogen bonds are found in the latter complexes. Correlations have been found between the relative energies of the sulfoxide versus the thioperoxide compounds and the transition state barriers. The geometry of the hydrogen bonds has been analyzed using a Steiner-Limbach relationship. (C) 2004 Elsevier Ltd. All rights reserved.

引用

页码：1391 / 1399

页数：9

共 34 条

[1] Discrimination of hydrogen-bonded complexes with axial chirality [J].