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Article: Density functional theory investigation of the reactions of isodihalomethanes (CH2X-X where X = Cl, Br, or I) with ethylene: Substituent effects on the carbenoid behavior of the CH2X-X species

TitleDensity functional theory investigation of the reactions of isodihalomethanes (CH2X-X where X = Cl, Br, or I) with ethylene: Substituent effects on the carbenoid behavior of the CH2X-X species
Authors
Issue Date2001
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/joc
Citation
Journal Of Organic Chemistry, 2001, v. 66 n. 17, p. 5890-5896 How to Cite?
AbstractWe investigated the chemical reactions of isodihalomethane (CH 2X-X) and CH 2X radical species (where X = Cl, Br, or I) with ethylene and the isomerization reactions of CH 2X-X using density functional theory calculations. The CH 2X-X species readily reacts with ethylene to give the cyclopropane product and an X 2 product via a one-step reaction with barrier heights of ̃2.9 kcal/mol for CH 2I-I, 6.8 kcal/mol for CH 2Br-Br, and 8.9 kcal/mol for CH 2Cl-Cl. The CH 2X reactions with ethylene proceed via a two-step reaction mechanism to give a cyclopropane product and X atom product with much larger barriers to reaction. This suggests that photocyclopropanation reactions using ultraviolet excitation of dihalomethanes most likely occurs via the isodihalomethane species and not the CH 2X species. The isomerization reactions of CH 2X-X had barrier heights of ̃14.4 kcal/mol for CH 2I-I, 11.8 kcal/mol for CH 2Br-Br, and 9.1 kcal/mol for CH 2Cl-Cl. We compare our results for the CH 2X-X carbenoids to results from previous calculations of the Simmons-Smith-type carbenoids (XCH 2ZnX) and Li-type carbenoids (LiCH 2X) and discuss their differences and similarities as methylene transfer agents.
Persistent Identifierhttp://hdl.handle.net/10722/167720
ISSN
2015 Impact Factor: 4.785
2015 SCImago Journal Rankings: 2.095
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorPhillips, DLen_US
dc.contributor.authorFang, WHen_US
dc.date.accessioned2012-10-08T03:10:24Z-
dc.date.available2012-10-08T03:10:24Z-
dc.date.issued2001en_US
dc.identifier.citationJournal Of Organic Chemistry, 2001, v. 66 n. 17, p. 5890-5896en_US
dc.identifier.issn0022-3263en_US
dc.identifier.urihttp://hdl.handle.net/10722/167720-
dc.description.abstractWe investigated the chemical reactions of isodihalomethane (CH 2X-X) and CH 2X radical species (where X = Cl, Br, or I) with ethylene and the isomerization reactions of CH 2X-X using density functional theory calculations. The CH 2X-X species readily reacts with ethylene to give the cyclopropane product and an X 2 product via a one-step reaction with barrier heights of ̃2.9 kcal/mol for CH 2I-I, 6.8 kcal/mol for CH 2Br-Br, and 8.9 kcal/mol for CH 2Cl-Cl. The CH 2X reactions with ethylene proceed via a two-step reaction mechanism to give a cyclopropane product and X atom product with much larger barriers to reaction. This suggests that photocyclopropanation reactions using ultraviolet excitation of dihalomethanes most likely occurs via the isodihalomethane species and not the CH 2X species. The isomerization reactions of CH 2X-X had barrier heights of ̃14.4 kcal/mol for CH 2I-I, 11.8 kcal/mol for CH 2Br-Br, and 9.1 kcal/mol for CH 2Cl-Cl. We compare our results for the CH 2X-X carbenoids to results from previous calculations of the Simmons-Smith-type carbenoids (XCH 2ZnX) and Li-type carbenoids (LiCH 2X) and discuss their differences and similarities as methylene transfer agents.en_US
dc.languageengen_US
dc.publisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/jocen_US
dc.relation.ispartofJournal of Organic Chemistryen_US
dc.titleDensity functional theory investigation of the reactions of isodihalomethanes (CH2X-X where X = Cl, Br, or I) with ethylene: Substituent effects on the carbenoid behavior of the CH2X-X speciesen_US
dc.typeArticleen_US
dc.identifier.emailPhillips, DL:phillips@hku.hken_US
dc.identifier.authorityPhillips, DL=rp00770en_US
dc.description.naturelink_to_subscribed_fulltexten_US
dc.identifier.doi10.1021/jo010582ien_US
dc.identifier.pmid11511267-
dc.identifier.scopuseid_2-s2.0-0035943286en_US
dc.identifier.hkuros73869-
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-0035943286&selection=ref&src=s&origin=recordpageen_US
dc.identifier.volume66en_US
dc.identifier.issue17en_US
dc.identifier.spage5890en_US
dc.identifier.epage5896en_US
dc.identifier.isiWOS:000170598900033-
dc.publisher.placeUnited Statesen_US
dc.identifier.scopusauthoridPhillips, DL=7404519365en_US
dc.identifier.scopusauthoridFang, WH=7202236871en_US

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