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- Publisher Website: 10.1021/ja030280t
- Scopus: eid_2-s2.0-84961979388
- PMID: 14653755
- WOS: WOS:000187007400049
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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
Title | Theoretical Study of Samarium (II) Carbenoid (ISmCH2I) Promoted Cyclopropanation Reactions with Ethylene and the Effect of THF Solvent on the Reaction Pathways |
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Authors | |
Issue Date | 2003 |
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, 2003, v. 125 n. 49, p. 15200-15209 How to Cite? |
Abstract | A 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 Identifier | http://hdl.handle.net/10722/167851 |
ISSN | 2023 Impact Factor: 14.4 2023 SCImago Journal Rankings: 5.489 |
ISI Accession Number ID | |
References |
DC Field | Value | Language |
---|---|---|
dc.contributor.author | Zhao, C | en_US |
dc.contributor.author | Wang, D | en_US |
dc.contributor.author | Phillips, DL | en_US |
dc.date.accessioned | 2012-10-08T03:12:13Z | - |
dc.date.available | 2012-10-08T03:12:13Z | - |
dc.date.issued | 2003 | en_US |
dc.identifier.citation | Journal Of The American Chemical Society, 2003, v. 125 n. 49, p. 15200-15209 | en_US |
dc.identifier.issn | 0002-7863 | en_US |
dc.identifier.uri | http://hdl.handle.net/10722/167851 | - |
dc.description.abstract | A 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.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 | Theoretical Study of Samarium (II) Carbenoid (ISmCH2I) Promoted Cyclopropanation Reactions with Ethylene and the Effect of THF Solvent on the Reaction Pathways | en_US |
dc.type | Article | en_US |
dc.identifier.email | Phillips, DL:phillips@hku.hk | en_US |
dc.identifier.authority | Phillips, DL=rp00770 | en_US |
dc.description.nature | link_to_subscribed_fulltext | en_US |
dc.identifier.doi | 10.1021/ja030280t | en_US |
dc.identifier.pmid | 14653755 | - |
dc.identifier.scopus | eid_2-s2.0-84961979388 | en_US |
dc.identifier.hkuros | 92459 | - |
dc.relation.references | http://www.scopus.com/mlt/select.url?eid=2-s2.0-0345098291&selection=ref&src=s&origin=recordpage | en_US |
dc.identifier.volume | 125 | en_US |
dc.identifier.issue | 49 | en_US |
dc.identifier.spage | 15200 | en_US |
dc.identifier.epage | 15209 | en_US |
dc.identifier.isi | WOS:000187007400049 | - |
dc.publisher.place | United States | en_US |
dc.identifier.scopusauthorid | Zhao, C=7403563836 | en_US |
dc.identifier.scopusauthorid | Wang, D=7407071795 | en_US |
dc.identifier.scopusauthorid | Phillips, DL=7404519365 | en_US |
dc.identifier.issnl | 0002-7863 | - |