title: Mechanistic aspects of the abstraction of an allylic hydrogen in the chlorine atom reaction with 2-methyl-1,3-butadiene (isoprene).
abstract: The different channels for the abstraction of an allylic hydrogen in the chlorine atom reaction with isoprene were explored using ab initio methodology. It is shown that the metathesis reaction proceeds through an association-elimination mechanism in which a weakly bound intermediate (HCl.C(5)H(7)(*)) is formed first (formal addition). Further evolution by HCl elimination leads to the final C(5)H(7)(*) radical. QCISD(T)/aug-cc-pVDZ//MP2/6-31G(d,p) calculations show that for two of the possible pathways the barrier heights involved are moderate and the formation of the intermediates are exergonic (DeltaG < 0). Therefore, the mechanism proposed is both kinetically and thermodynamically feasible. The pressure dependence experimentally observed for the Cl + isoprene reaction can be rationalized in terms of the association-elimination mechanism proposed.
authors.affiliation: Laboratorio de Química Computacional, Departamento de Química Física y Analítica, Facultad de Química, Universidad de Oviedo, Oviedo, Principado de Asturias, Spain.
authors.forename: P
authors.initials: P
authors.lastname: Braña
authors.forename: J A
authors.initials: JA
authors.lastname: Sordo
mesh_terms: D002070:Butadienes / Q000737:chemistry* / Q000378:metabolism; D002713:Chlorine / Q000737:chemistry* / Q000378:metabolism; D045782:Hemiterpenes; D006859:Hydrogen / Q000737:chemistry*; D008956:Models, Chemical; D008958:Models, Molecular; D010420:Pentanes; D010839:Phytoplankton / Q000378:metabolism
chemical_list: D002070:Butadienes; D045782:Hemiterpenes; D010420:Pentanes; C005059:isoprene; D002713:Chlorine; D006859:Hydrogen