Jump to main content
Jump to site search

Issue 6, 2001
Previous Article Next Article

Theoretical studies on thiocarbonyl group transfer reactions

Author affiliations


The gas-phase thiocarbonyl transfer reactions X  + RC([double bond, length half m-dash]S)Z ⇌ RC([double bond, length half m-dash]S)X + Z have been investigated with X, Z = Cl, Br and R = H, CH3 at the MP2 and G2(+) levels using the MP2/6-311+G** optimized geometries. The thiocarbonyl transfers proceed by a stepwise mechanism through a triple-well potential energy surface involving a tetrahedral intermediate, T. The strong proclivity toward the stepwise path is caused mainly by the low-lying πC[double bond, length half m-dash]S* level coupled with the high energy σC–Z* orbital. The reaction barriers, ΔG, are higher than the corresponding values for the carbonyl transfers, excepting for the X = Z = Cl case at the G2(+) level. The major factors for these elevated barriers, despite the low deformation energies (ΔEdef), are lower proximate σ–σ* charge transfer energies (δΔEσ–σ*(2)) and the relatively high electrostatic repulsion (ΔEes > 0) in the transition state due to the highly polarized structure with a large negative charge on the S atom. The occurrence of a well-defined intermediate, T, in the reaction coordinate leads to a relatively early transition state with a low degree of bond making and breaking in the transition state.

Back to tab navigation

Supplementary files

Article information

18 Dec 2000
28 Feb 2001
First published
30 Apr 2001

New J. Chem., 2001,25, 859-863
Article type

Theoretical studies on thiocarbonyl group transfer reactions

C. K. Sohn, E. K. Ma, C. K. Kim, H. W. Lee and I. Lee, New J. Chem., 2001, 25, 859
DOI: 10.1039/B010202O

Social activity

Search articles by author