A chemical dynamics, kinetics, and theoretical study on the reaction of the cyano radical (CN; X(2)Sigma+) with phenylacetylene (C6H5CCH; X(1)A1).

Abstract : The chemical reaction dynamics to form o-, m-, and p-cyanophenylacetylene via the neutral-neutral reaction of ground state cyano radicals with phenylacetylene and D(1)-phenylacetylene were investigated in crossed beam experiments; these studies were combined with kinetics measurements of the rate coefficients at temperatures of 123, 200, and 298 K and supplemented by electronic structure calculations. The data suggest that the reaction is initiated by a barrier-less addition of the electrophilic cyano radical to the o-, m-, or p-position of the aromatic ring. The eventually fragmented via atomic hydrogen elimination to form o-, m-, and p-cyanophenylacetylene via tight exit transition states with the hydrogen atom being ejected almost perpendicularly to the molecular plane of the rotating complex. The overall reaction to form o-, m-, and p-cyanophenylacetylene was found to be exoergic by 89 +/- 18 kJ mol(-1) in nice agreement with the calculations. The o-cyanophenylacetylene isomer is of particular relevance as a potential building block to the formation of nitrogen-substituted didehydronaphthalene molecules in analogy to didehydronaphthalene in Titan's aerosol layers--a pathway hitherto neglected by the planetary science modeling community.
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Submitted on : Tuesday, September 18, 2012 - 9:49:29 AM
Last modification on : Thursday, August 1, 2019 - 10:42:20 AM

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Chris J. Bennett, Sébastien B. Morales, Sébastien D. Le Picard, André Canosa, Ian R Sims, et al.. A chemical dynamics, kinetics, and theoretical study on the reaction of the cyano radical (CN; X(2)Sigma+) with phenylacetylene (C6H5CCH; X(1)A1).. Physical Chemistry Chemical Physics, Royal Society of Chemistry, 2010, 12 (31), pp.8737-49. ⟨10.1039/b925072g⟩. ⟨hal-00733144⟩

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