TY - JOUR

T1 - A crossed molecular beam and ab initio study on the formation of 5-and 6-methyl-1, 4-dihydronaphthalene (C 11 H 12) via the reaction of meta-tolyl (C 7 H 7) with 1, 3-butadiene (C 4 H 6)

AU - Muzangwa, Lloyd G

AU - Yang, Tao

AU - Parker, Dorian SN

AU - Kaiser, Ralf I

AU - Mebel, Alexander M

AU - Jamal, Adeel

AU - Ryazantsev, Mikhail

AU - Morokuma, Keiji

PY - 2015

Y1 - 2015

N2 - The crossed molecular beam reactions of the meta-tolyl radical with 1,3-butadiene and D6-1,3-butadiene were conducted at collision energies of 48.5 kJ mol−1 and 51.7 kJ mol−1. The reaction dynamics propose a complex-forming reaction mechanism via addition of the meta-tolyl radical with its radical center either to the C1 or C2 carbon atom of the 1,3-butadiene reactant forming two distinct intermediates, which are connected via migration of the meta-tolyl group. Considering addition to C1 proceeds by formation of a van-der-Waals complex below the energy of the separated reactants, we propose that in cold molecular clouds holding temperatures as low as 10 K, the reaction of the meta-tolyl radical with 1,3-butadiene is de-facto barrier less. At elevated temperatures such as in combustion processes, the reaction can also proceed via addition to C2 by overcoming the entrance barrier to addition (11 kJ mol−1). Eventually, the resonantly stabilized free radical intermediate C11H13 undergoes isomerization to a cis fo

AB - The crossed molecular beam reactions of the meta-tolyl radical with 1,3-butadiene and D6-1,3-butadiene were conducted at collision energies of 48.5 kJ mol−1 and 51.7 kJ mol−1. The reaction dynamics propose a complex-forming reaction mechanism via addition of the meta-tolyl radical with its radical center either to the C1 or C2 carbon atom of the 1,3-butadiene reactant forming two distinct intermediates, which are connected via migration of the meta-tolyl group. Considering addition to C1 proceeds by formation of a van-der-Waals complex below the energy of the separated reactants, we propose that in cold molecular clouds holding temperatures as low as 10 K, the reaction of the meta-tolyl radical with 1,3-butadiene is de-facto barrier less. At elevated temperatures such as in combustion processes, the reaction can also proceed via addition to C2 by overcoming the entrance barrier to addition (11 kJ mol−1). Eventually, the resonantly stabilized free radical intermediate C11H13 undergoes isomerization to a cis fo

KW - http://pubs.rsc.org/en/content/articlehtml/2015/cp/c5cp00311c

U2 - 10.1039/C5CP00311C

DO - 10.1039/C5CP00311C

M3 - Article

VL - 17

SP - 7699

EP - 7706

JO - Physical Chemistry Chemical Physics

JF - Physical Chemistry Chemical Physics

SN - 1463-9076

IS - 12

ER -