Title: Condensation reactions between 1,3-butadiene radical cation and acetylene in the gas phase
Authors: Bouchoux, G ×
Nguyen, Minh Tho
Salpin, JY #
Issue Date: 2000
Series Title: Journal of Physical Chemistry A vol:104 issue:24 pages:5778-5786
Conference: date:Ecole Polytech, CNRS, UMR 7651, Lab Mecan React, F-91128 Palaiseau, France; Katholieke Univ Leuven, Dept Chem, B-3001 Louvain, Belgium
Abstract: The present paper reports the first experimental and theoretical results concerning the reaction of [1,3-butadiene](+.) radical cation, I, with neutral acetylene C2H2, 2. Experiments conducted in the gas phase and under low pressure in an FT-ICR mass spectrometer show that the reaction leads to C6H7+ ions. Complete analysis of the experimental data reveals that a mixture of three distinct C6H7+ species is produced: it consists of benzenium ions, a (approximate to 55%), and the two most stable protonated forms of fulvene (i.e., a-protonated fulvene, b. approximate to 25%, and bicyclo[3,1,0]-hexenyl, c, approximate to 20%). A mechanism, supported by ab initio molecular orbital calculations at the UMP2/6-311+G(d,p)//UMP2/6-31G(d) + ZPE level, is proposed to account for the observations. A Diels-Alder type reaction involving stepwise bond formation is at the origin of ionized 1,4-cyclohexadiene, 5, the first precursor of the benzenium ion a. Starting from 5, hydrogen-atom migrations and ring-contraction processes generate the precursors of the two other products, b and c.
ISSN: 1089-5639
Publication status: published
KU Leuven publication type: IT
Appears in Collections:Quantum Chemistry and Physical Chemistry Section
× corresponding author
# (joint) last author

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