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Please use this identifier to cite or link to this item: http://hdl.handle.net/1942/2238

Title: Theoretical study of the internal elimination reactions of xanthate precursors
Authors: CLAES, Luc
FRANCOIS, Jean-Pierre
DELEUZE, Michael
Issue Date: 2003
Citation: JOURNAL OF COMPUTATIONAL CHEMISTRY, 24(16). p. 2023-2031
Abstract: The gas-phase internal elimination (E-i) reaction of ethyl xanthate (CH3-CH2-S-CS-O-CH3) has been investigated by means of Hartree-Fock, second-order Moller-Plesset, and density functional theory (DFT) using the Becke three-parameter Lee-Yang-Parr (B3LYP) functional and the modified Perdew-Wang one-parameter model for kinetics (MPW1K). Considerable differences between the ground- and transition-state geometries and the calculated activation energies are observed from one approach to the other, which justifies first a careful calibration of the methods against the results of benchmark CCSD(T) calculations. Compared with these, DFT calculations along with the MPW1K functional are found to be an appropriate choice for describing the E-i reaction of xanthate precursors. The precursor conformation and the transition states involved in the internal conversion of xanthate precursors of cyano derivatives of ethylene, and of cis- and trans-stilbene, are then characterized in detail by means of this functional. (C) 2003 Wiley Periodicals, Inc.
Notes: Limburgs Univ Ctr, Dept SBG, B-3590 Diepenbeek, Belgium.Deleuze, MS, Limburgs Univ Ctr, Dept SBG, Univ Campus, B-3590 Diepenbeek, Belgium.
URI: http://hdl.handle.net/1942/2238
DOI: 10.1002/jcc.10358
ISI #: 000186375200007
ISSN: 0192-8651
Category: A1
Type: Journal Contribution
Validation: ecoom, 2004
Appears in Collections: Research publications

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