Molecular mechanisms in the pyrolysis of unsaturated chlorinated hydrocarbons: formation of benzene rings. 1. Quantum chemical studies.

Show simple item record McIntosh, Grant en Russell, Douglas K en 2018-10-17T00:51:27Z en 2013-05-09 en
dc.identifier.issn 1089-5639 en
dc.identifier.uri en
dc.description.abstract Analogues of important aromatic growth mechanisms in hydrocarbon pyrolysis and combustion systems are extended to chlorinated systems. We consider the addition of C2Cl2 to both C4Cl3 and C4Cl5 radicals at the M06-2X/6-311+G(3df,3p)//B3LYP/6-31G(d) level of theory, and we demonstrate that these reaction systems have much in common with those of nonchlorinated species. In particular, we find that these radicals appear to lead preferentially to fulvenes, and not to the observed aromatic products, as is found in nonchlorinated systems. We have therefore also considered nonradical C4/C2 channels by way of Diels-Alder cyclization of C4Cl4/C2Cl2 and C4H2Cl2/C2HCl pairs to describe aromatic formation. While the latter pair readily leads to the formation of partially chlorinated benzenes, the fully chlorinated congeners are sterically prohibited from ring closing directly; this leads to a series of novel rearrangement processes which predict the formation of hexachloro-1,5-diene-3-yne, in addition to hexachlorobenzene, in good agreement with experiment. This suggests, for the first time, that facile nonradical routes to aromatic formation are operative in partially and fully chlorinated pyrolysis and combustion systems. en
dc.format.medium Print-Electronic en
dc.language eng en
dc.relation.ispartofseries The journal of physical chemistry. A en
dc.rights Items in ResearchSpace are protected by copyright, with all rights reserved, unless otherwise indicated. Previously published items are made available in accordance with the copyright policy of the publisher. en
dc.rights.uri en
dc.subject Benzene en
dc.subject Hydrocarbons, Chlorinated en
dc.subject Molecular Structure en
dc.subject Kinetics en
dc.subject Quantum Theory en
dc.title Molecular mechanisms in the pyrolysis of unsaturated chlorinated hydrocarbons: formation of benzene rings. 1. Quantum chemical studies. en
dc.type Journal Article en
dc.identifier.doi 10.1021/jp3120379 en
pubs.issue 20 en
pubs.begin-page 4183 en
pubs.volume 117 en
dc.rights.holder Copyright: The author en
dc.identifier.pmid 23597165 en
pubs.end-page 4197 en
pubs.publication-status Published en
dc.rights.accessrights en
pubs.subtype Research Support, Non-U.S. Gov't en
pubs.subtype Journal Article en
pubs.elements-id 380342 en
dc.identifier.eissn 1520-5215 en
pubs.record-created-at-source-date 2013-05-23 en
pubs.dimensions-id 23597165 en

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