Density functional theory study of CS2/Cl adducts and their isomerization reactions

Abstract

Density functional theory calculations are presented for the formation and isomerization of CS2/Cl complexes. The S=C=S⋯Cl complex can be produced readily, but the SC(Cl)S complex is difficult to make directly with a barrier to reaction of 17.8 kcal/mol. The isomerization of S=C=S⋯Cl into the SC(Cl)S adduct has a barrier of 13.2 kcal/mol. Therefore, the SC(Cl)S adduct probably forms via first production of the S=C=S⋯Cl complex and subsequent isomerization to SC(Cl)S. Cl atom reaction with either the S=C=S⋯Cl and SC(Cl)S species provides a radical initiated isomerization reaction to give the other species with much lower barriers to isomerization (about 1.4-2.6 kcal/mol). © 2002 Elsevier Science B.V. All rights reserved.