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- Publisher Website: 10.1021/ja050891g
- Scopus: eid_2-s2.0-22144470478
- PMID: 15998095
- WOS: WOS:000230434200046
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Article: Computational studies of the thermal fragmentation of P-arylphosphiranes: Have arylphosphinidenes been generated by this method?
Title | Computational studies of the thermal fragmentation of P-arylphosphiranes: Have arylphosphinidenes been generated by this method? |
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Authors | |
Issue Date | 2005 |
Publisher | American 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? |
Abstract | CASSCF, 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 Identifier | http://hdl.handle.net/10722/167939 |
ISSN | 2023 Impact Factor: 14.4 2023 SCImago Journal Rankings: 5.489 |
ISI Accession Number ID | |
References |
DC Field | Value | Language |
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dc.contributor.author | Lam, WH | en_US |
dc.contributor.author | Gaspar, PP | en_US |
dc.contributor.author | Hrovat, DA | en_US |
dc.contributor.author | Trieber Ii, DA | en_US |
dc.contributor.author | Davidson, ER | en_US |
dc.contributor.author | Borden, WT | en_US |
dc.date.accessioned | 2012-10-08T03:13:09Z | - |
dc.date.available | 2012-10-08T03:13:09Z | - |
dc.date.issued | 2005 | en_US |
dc.identifier.citation | Journal Of The American Chemical Society, 2005, v. 127 n. 27, p. 9886-9894 | en_US |
dc.identifier.issn | 0002-7863 | en_US |
dc.identifier.uri | http://hdl.handle.net/10722/167939 | - |
dc.description.abstract | CASSCF, 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.language | eng | en_US |
dc.publisher | American Chemical Society. The Journal's web site is located at http://pubs.acs.org/journals/jacsat/index.html | en_US |
dc.relation.ispartof | Journal of the American Chemical Society | en_US |
dc.title | Computational studies of the thermal fragmentation of P-arylphosphiranes: Have arylphosphinidenes been generated by this method? | en_US |
dc.type | Article | en_US |
dc.identifier.email | Lam, WH:chsue@hku.hk | en_US |
dc.identifier.authority | Lam, WH=rp00719 | en_US |
dc.description.nature | link_to_subscribed_fulltext | en_US |
dc.identifier.doi | 10.1021/ja050891g | en_US |
dc.identifier.pmid | 15998095 | - |
dc.identifier.scopus | eid_2-s2.0-22144470478 | en_US |
dc.relation.references | http://www.scopus.com/mlt/select.url?eid=2-s2.0-22144470478&selection=ref&src=s&origin=recordpage | en_US |
dc.identifier.volume | 127 | en_US |
dc.identifier.issue | 27 | en_US |
dc.identifier.spage | 9886 | en_US |
dc.identifier.epage | 9894 | en_US |
dc.identifier.isi | WOS:000230434200046 | - |
dc.publisher.place | United States | en_US |
dc.identifier.scopusauthorid | Lam, WH=26642862800 | en_US |
dc.identifier.scopusauthorid | Gaspar, PP=7007160816 | en_US |
dc.identifier.scopusauthorid | Hrovat, DA=7005268670 | en_US |
dc.identifier.scopusauthorid | Trieber II, DA=6506674320 | en_US |
dc.identifier.scopusauthorid | Davidson, ER=7402237753 | en_US |
dc.identifier.scopusauthorid | Borden, WT=35495118300 | en_US |
dc.identifier.issnl | 0002-7863 | - |