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.author | Coote, Michelle | |
---|---|---|
dc.contributor.author | Davis, Thomas P | |
dc.contributor.author | Radom, Leo | |
dc.date.accessioned | 2015-12-13T23:35:08Z | |
dc.identifier.issn | 0024-9297 | |
dc.identifier.uri | http://hdl.handle.net/1885/93771 | |
dc.description.abstract | 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 structure. The implications of these results for the penultimate unit effect in free-radical copolymerization are discussed. | |
dc.publisher | American Chemical Society | |
dc.source | Macromolecules | |
dc.subject | Keywords: Addition reactions; Copolymerization; Electron energy levels; Free radicals; Mathematical models; Olefins; Molecular orbitals; Penultimate unit effect; Free radical polymerization | |
dc.title | Conformational dependence of the penultimate unit effect in free-radical copolymerization | |
dc.type | Journal article | |
local.description.notes | Imported from ARIES | |
local.description.refereed | Yes | |
local.identifier.citationvolume | 32 | |
dc.date.issued | 1999 | |
local.identifier.absfor | 030601 - Catalysis and Mechanisms of Reactions | |
local.identifier.ariespublication | MigratedxPub25177 | |
local.type.status | Published Version | |
local.contributor.affiliation | Coote, Michelle, College of Physical and Mathematical Sciences, ANU | |
local.contributor.affiliation | Davis, Thomas P, University of New South Wales | |
local.contributor.affiliation | Radom, Leo, College of Physical and Mathematical Sciences, ANU | |
local.description.embargo | 2037-12-31 | |
local.bibliographicCitation.startpage | 5270?5276 | |
dc.date.updated | 2015-12-12T09:38:48Z | |
local.identifier.scopusID | 2-s2.0-0032620354 | |
Collections | ANU Research Publications |
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