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Theoretical approach to the mechanism of reactions between halogen atoms and unsaturated hydrocarbons: The Cl + propene reaction
Author(s) -
Braña Pedro,
Sordo José A.
Publication year - 2003
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.10360
Subject(s) - propene , chemistry , halogen , abstraction , mechanism (biology) , radical , reaction mechanism , computational chemistry , kinetic energy , potential energy surface , thermodynamics , ab initio , physics , organic chemistry , catalysis , quantum mechanics , philosophy , alkyl , epistemology
The potential energy surface for the Cl + propene reaction was analyzed at the MP2 level using Pople's 6‐31G( d , p ) and 6‐311+G( d , p ), and Dunning's cc‐pVDZ and aug‐cc‐pVDZ basis sets. Two different channels for the addition reaction leading to chloroalkyl radicals and five alternative channels for the abstraction reaction leading to C 3 H 5 ·+ HCl were explored. The corresponding energy profiles were computed at the QCISD(T)/aug‐cc‐pVDZ//MP2/aug‐cc‐pVDZ level of theory. Theoretical results suggest that the previously established mechanism consisting of (1) direct abstraction and (2) addition–elimination steps is instead made up of (1) addition through an intermediate and (2) two‐step abstraction processes. No direct abstraction mechanism exists on the potential energy surface. The kinetic equations derived for the new mechanism are consistent with the pressure dependence experimentally observed for this reaction. © 2003 Wiley Periodicals, Inc. J Comput Chem 24: 2044–2062, 2003