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Article: Theoretical Study of Samarium (II) Carbenoid (ISmCH2I) Promoted Cyclopropanation Reactions with Ethylene and the Effect of THF Solvent on the Reaction Pathways

TitleTheoretical Study of Samarium (II) Carbenoid (ISmCH2I) Promoted Cyclopropanation Reactions with Ethylene and the Effect of THF Solvent on the Reaction Pathways
Authors
Issue Date2003
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, 2003, v. 125 n. 49, p. 15200-15209 How to Cite?
AbstractA computational study of the cyclopropanation reactions of divalent samarium carbenoid ISmCH2I with ethylene is presented. The reaction proceeds through two competing pathways: methylene transfer and carbometalation. The ISmCH2I species was found to have a "samarium carbene complex" character with properties similar to previously investigated lithium carbenoids (LiCH2X where X = CI, Br, I). The ISmCH 2I carbenoid was found to be noticeably different in structure with more electrophilic character and higher chemical reactivity than the closely related classical Simmons-Smith (IZnCH2I) carbenoid. The effect of THF solvent was investigated by explicit coordination of the solvent THF molecules to the Sm (II) center in the carbenoid. The ISmCH 2I/(THF)n (where n = 0, 1, 2) carbenoid methylene transfer pathway barriers to reaction become systematically lower as more THF solvent is added (from 12.9 to 14.5 kcal/mol for no THF molecules to 8.8 to 10. 7 kcal/mol for two THF molecules). In contrast, the reaction barriers for cyclopropanation via the carbometalation pathway remain high (> 15 kcal/mol). The computational results are briefly compared to other carbenoid reactions and related species.
Persistent Identifierhttp://hdl.handle.net/10722/167851
ISSN
2015 Impact Factor: 13.038
2015 SCImago Journal Rankings: 7.123
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorZhao, Cen_US
dc.contributor.authorWang, Den_US
dc.contributor.authorPhillips, DLen_US
dc.date.accessioned2012-10-08T03:12:13Z-
dc.date.available2012-10-08T03:12:13Z-
dc.date.issued2003en_US
dc.identifier.citationJournal Of The American Chemical Society, 2003, v. 125 n. 49, p. 15200-15209en_US
dc.identifier.issn0002-7863en_US
dc.identifier.urihttp://hdl.handle.net/10722/167851-
dc.description.abstractA computational study of the cyclopropanation reactions of divalent samarium carbenoid ISmCH2I with ethylene is presented. The reaction proceeds through two competing pathways: methylene transfer and carbometalation. The ISmCH2I species was found to have a "samarium carbene complex" character with properties similar to previously investigated lithium carbenoids (LiCH2X where X = CI, Br, I). The ISmCH 2I carbenoid was found to be noticeably different in structure with more electrophilic character and higher chemical reactivity than the closely related classical Simmons-Smith (IZnCH2I) carbenoid. The effect of THF solvent was investigated by explicit coordination of the solvent THF molecules to the Sm (II) center in the carbenoid. The ISmCH 2I/(THF)n (where n = 0, 1, 2) carbenoid methylene transfer pathway barriers to reaction become systematically lower as more THF solvent is added (from 12.9 to 14.5 kcal/mol for no THF molecules to 8.8 to 10. 7 kcal/mol for two THF molecules). In contrast, the reaction barriers for cyclopropanation via the carbometalation pathway remain high (> 15 kcal/mol). The computational results are briefly compared to other carbenoid reactions and related species.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.titleTheoretical Study of Samarium (II) Carbenoid (ISmCH2I) Promoted Cyclopropanation Reactions with Ethylene and the Effect of THF Solvent on the Reaction Pathwaysen_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/ja030280ten_US
dc.identifier.pmid14653755-
dc.identifier.scopuseid_2-s2.0-0345098291en_US
dc.identifier.hkuros92459-
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-0345098291&selection=ref&src=s&origin=recordpageen_US
dc.identifier.volume125en_US
dc.identifier.issue49en_US
dc.identifier.spage15200en_US
dc.identifier.epage15209en_US
dc.identifier.isiWOS:000187007400049-
dc.publisher.placeUnited Statesen_US
dc.identifier.scopusauthoridZhao, C=7403563836en_US
dc.identifier.scopusauthoridWang, D=7407071795en_US
dc.identifier.scopusauthoridPhillips, DL=7404519365en_US

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