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Conformational dependence of the penultimate unit effect in free-radical copolymerization

Coote, Michelle; Davis, Thomas P; Radom, Leo

Description

The reaction barriers for the addition of various gamma-substituted propyl radicals to alkenes were obtained via ab initio molecular orbital calculations. The reactions studied were the additions of 3X-propyl (X = H, F) to CH2=CHF, 3X-propyl (X = H, CN) to CH2=CHCN, and 3X-propyl (X = H, CN) to CH2=CHNH2. The results indicate that the gamma substituent effect (i.e., penultimate unit effect) on the reaction barrier is strongly dependent on the conformations of the reacting radical and transition...[Show more]

dc.contributor.authorCoote, Michelle
dc.contributor.authorDavis, Thomas P
dc.contributor.authorRadom, Leo
dc.date.accessioned2015-12-13T23:35:08Z
dc.identifier.issn0024-9297
dc.identifier.urihttp://hdl.handle.net/1885/93771
dc.description.abstractThe reaction barriers for the addition of various gamma-substituted propyl radicals to alkenes were obtained via ab initio molecular orbital calculations. The reactions studied were the additions of 3X-propyl (X = H, F) to CH2=CHF, 3X-propyl (X = H, CN) to CH2=CHCN, and 3X-propyl (X = H, CN) to CH2=CHNH2. The results indicate that the gamma substituent effect (i.e., penultimate unit effect) on the reaction barrier is strongly dependent on the conformations of the reacting radical and transition structure. The implications of these results for the penultimate unit effect in free-radical copolymerization are discussed.
dc.publisherAmerican Chemical Society
dc.sourceMacromolecules
dc.subjectKeywords: Addition reactions; Copolymerization; Electron energy levels; Free radicals; Mathematical models; Olefins; Molecular orbitals; Penultimate unit effect; Free radical polymerization
dc.titleConformational dependence of the penultimate unit effect in free-radical copolymerization
dc.typeJournal article
local.description.notesImported from ARIES
local.description.refereedYes
local.identifier.citationvolume32
dc.date.issued1999
local.identifier.absfor030601 - Catalysis and Mechanisms of Reactions
local.identifier.ariespublicationMigratedxPub25177
local.type.statusPublished Version
local.contributor.affiliationCoote, Michelle, College of Physical and Mathematical Sciences, ANU
local.contributor.affiliationDavis, Thomas P, University of New South Wales
local.contributor.affiliationRadom, Leo, College of Physical and Mathematical Sciences, ANU
local.description.embargo2037-12-31
local.bibliographicCitation.startpage5270?5276
dc.date.updated2015-12-12T09:38:48Z
local.identifier.scopusID2-s2.0-0032620354
CollectionsANU Research Publications

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