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Article: Computational studies of the thermal fragmentation of P-arylphosphiranes: Have arylphosphinidenes been generated by this method?

TitleComputational studies of the thermal fragmentation of P-arylphosphiranes: Have arylphosphinidenes been generated by this method?
Authors
Issue Date2005
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/journals/jacsat/index.html
Citation
Journal Of The American Chemical Society, 2005, v. 127 n. 27, p. 9886-9894 How to Cite?
AbstractCASSCF, CASPT2, CCSD(T), and (U)B3LYP electronic structure calculations have been performed in order to investigate the thermal fragmentation of P-phenylphosphirane (1) to phenylphosphinidene (PhP) and ethylene. The calculations show that generation of triplet PhP via a stepwise pathway is 21 kcal mol-1 less endothermic and has a 12 kcal mol-1 lower barrier height than concerted fragmentation of 1 to give singlet PhP. The formation of singlet PhP via a concerted pathway is predicted to be stereospecific, whereas formation of triplet PhP is predicted to occur with complete loss of stereochemistry. However, calculations on fragmentation of anti-cis-2,3-dimethyl-P-mesitylphosphirane (cis-1Me) to triplet mesitylphosphinidene (MesP) indicate that this reaction should be more stereospecific, in agreement with the experimental results of Li and Caspar. Nevertheless, with a predicted free energy of activation of 42 kcal mol -1, the formation of MesP from cis-1Me is not likely to have occurred in an uncatalyzed reaction at the temperatures at which this phosphirane has been pyrolyzed. © 2005 American Chemical Society.
Persistent Identifierhttp://hdl.handle.net/10722/167939
ISSN
2015 Impact Factor: 13.038
2015 SCImago Journal Rankings: 7.123
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorLam, WHen_US
dc.contributor.authorGaspar, PPen_US
dc.contributor.authorHrovat, DAen_US
dc.contributor.authorTrieber Ii, DAen_US
dc.contributor.authorDavidson, ERen_US
dc.contributor.authorBorden, WTen_US
dc.date.accessioned2012-10-08T03:13:09Z-
dc.date.available2012-10-08T03:13:09Z-
dc.date.issued2005en_US
dc.identifier.citationJournal Of The American Chemical Society, 2005, v. 127 n. 27, p. 9886-9894en_US
dc.identifier.issn0002-7863en_US
dc.identifier.urihttp://hdl.handle.net/10722/167939-
dc.description.abstractCASSCF, CASPT2, CCSD(T), and (U)B3LYP electronic structure calculations have been performed in order to investigate the thermal fragmentation of P-phenylphosphirane (1) to phenylphosphinidene (PhP) and ethylene. The calculations show that generation of triplet PhP via a stepwise pathway is 21 kcal mol-1 less endothermic and has a 12 kcal mol-1 lower barrier height than concerted fragmentation of 1 to give singlet PhP. The formation of singlet PhP via a concerted pathway is predicted to be stereospecific, whereas formation of triplet PhP is predicted to occur with complete loss of stereochemistry. However, calculations on fragmentation of anti-cis-2,3-dimethyl-P-mesitylphosphirane (cis-1Me) to triplet mesitylphosphinidene (MesP) indicate that this reaction should be more stereospecific, in agreement with the experimental results of Li and Caspar. Nevertheless, with a predicted free energy of activation of 42 kcal mol -1, the formation of MesP from cis-1Me is not likely to have occurred in an uncatalyzed reaction at the temperatures at which this phosphirane has been pyrolyzed. © 2005 American Chemical Society.en_US
dc.languageengen_US
dc.publisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/journals/jacsat/index.htmlen_US
dc.relation.ispartofJournal of the American Chemical Societyen_US
dc.titleComputational studies of the thermal fragmentation of P-arylphosphiranes: Have arylphosphinidenes been generated by this method?en_US
dc.typeArticleen_US
dc.identifier.emailLam, WH:chsue@hku.hken_US
dc.identifier.authorityLam, WH=rp00719en_US
dc.description.naturelink_to_subscribed_fulltexten_US
dc.identifier.doi10.1021/ja050891gen_US
dc.identifier.pmid15998095-
dc.identifier.scopuseid_2-s2.0-22144470478en_US
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-22144470478&selection=ref&src=s&origin=recordpageen_US
dc.identifier.volume127en_US
dc.identifier.issue27en_US
dc.identifier.spage9886en_US
dc.identifier.epage9894en_US
dc.identifier.isiWOS:000230434200046-
dc.publisher.placeUnited Statesen_US
dc.identifier.scopusauthoridLam, WH=26642862800en_US
dc.identifier.scopusauthoridGaspar, PP=7007160816en_US
dc.identifier.scopusauthoridHrovat, DA=7005268670en_US
dc.identifier.scopusauthoridTrieber II, DA=6506674320en_US
dc.identifier.scopusauthoridDavidson, ER=7402237753en_US
dc.identifier.scopusauthoridBorden, WT=35495118300en_US

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