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Article: A density functional theory study of aluminum carbenoid (CH 3)2A1CH2X (X = Cl, Br, I) promoted cyclopropanation reactions compared to IMCH2i (M = Li, Sm, Zn) carbenoids

TitleA density functional theory study of aluminum carbenoid (CH 3)2A1CH2X (X = Cl, Br, I) promoted cyclopropanation reactions compared to IMCH2i (M = Li, Sm, Zn) carbenoids
Authors
Issue Date2006
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/organometallics
Citation
Organometallics, 2006, v. 25 n. 15, p. 3735-3742 How to Cite?
AbstractDensity functional theory calculations are reported for the cyclopropanation reactions of selected aluminum carbenoids with ethylene for two reaction channels: methylene transfer and carbometalation. The aluminum carbenoids react with ethylene via an asynchronous attack on one CH2 group of ethylene with a relatively high barrier (11-15 kcal/mol). In contrast, the reaction barriers for cyclopropanation via the carbometalation are much higher (about 30 kcal/mol). These computational results are in good agreement with experimental results, and this suggests that the methylene transfer process is favored and the competition from the carbometalation pathway is negligible. The (CH3)2AlCH2Cl carbenoid (reaction barrier of 11.3 kcal/mol) is found to be the most reactive carbenoid in the (CH3)2AlCH2X (X = Cl, Br, I) series of carbenoids, and the (CH3)2AlCH2I carbenoid is the least reactive one. The present computational results are briefly compared with previously reported results for related lithium, samarium, and zinc carbenoids. The trend of the cyclopropanation reaction barrier of the carbenoids compared is LiCH2I (6.8 kcal/mol) ≈ ISmCH2I (5.5 kcal /mol) < (CH3)2AlCH2I (12.8 kcal/mol) < IZnCH2I (21.2 kcat/mol). These results are qualitatively consistent with the agreement between carbenoid character and experimental conditions needed for efficient reaction. © 2006 American Chemical Society.
Persistent Identifierhttp://hdl.handle.net/10722/168031
ISSN
2015 Impact Factor: 4.186
2015 SCImago Journal Rankings: 2.043
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorLi, ZHen_US
dc.contributor.authorKe, Zen_US
dc.contributor.authorZhao, Cen_US
dc.contributor.authorGeng, ZYen_US
dc.contributor.authorWang, YCen_US
dc.contributor.authorPhillips, DLen_US
dc.date.accessioned2012-10-08T03:14:22Z-
dc.date.available2012-10-08T03:14:22Z-
dc.date.issued2006en_US
dc.identifier.citationOrganometallics, 2006, v. 25 n. 15, p. 3735-3742en_US
dc.identifier.issn0276-7333en_US
dc.identifier.urihttp://hdl.handle.net/10722/168031-
dc.description.abstractDensity functional theory calculations are reported for the cyclopropanation reactions of selected aluminum carbenoids with ethylene for two reaction channels: methylene transfer and carbometalation. The aluminum carbenoids react with ethylene via an asynchronous attack on one CH2 group of ethylene with a relatively high barrier (11-15 kcal/mol). In contrast, the reaction barriers for cyclopropanation via the carbometalation are much higher (about 30 kcal/mol). These computational results are in good agreement with experimental results, and this suggests that the methylene transfer process is favored and the competition from the carbometalation pathway is negligible. The (CH3)2AlCH2Cl carbenoid (reaction barrier of 11.3 kcal/mol) is found to be the most reactive carbenoid in the (CH3)2AlCH2X (X = Cl, Br, I) series of carbenoids, and the (CH3)2AlCH2I carbenoid is the least reactive one. The present computational results are briefly compared with previously reported results for related lithium, samarium, and zinc carbenoids. The trend of the cyclopropanation reaction barrier of the carbenoids compared is LiCH2I (6.8 kcal/mol) ≈ ISmCH2I (5.5 kcal /mol) < (CH3)2AlCH2I (12.8 kcal/mol) < IZnCH2I (21.2 kcat/mol). These results are qualitatively consistent with the agreement between carbenoid character and experimental conditions needed for efficient reaction. © 2006 American Chemical Society.en_US
dc.languageengen_US
dc.publisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/organometallicsen_US
dc.relation.ispartofOrganometallicsen_US
dc.titleA density functional theory study of aluminum carbenoid (CH 3)2A1CH2X (X = Cl, Br, I) promoted cyclopropanation reactions compared to IMCH2i (M = Li, Sm, Zn) carbenoidsen_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/om060333qen_US
dc.identifier.scopuseid_2-s2.0-33746355989en_US
dc.identifier.hkuros131934-
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-33746355989&selection=ref&src=s&origin=recordpageen_US
dc.identifier.volume25en_US
dc.identifier.issue15en_US
dc.identifier.spage3735en_US
dc.identifier.epage3742en_US
dc.identifier.isiWOS:000238848600032-
dc.publisher.placeUnited Statesen_US
dc.identifier.scopusauthoridLi, ZH=26643181000en_US
dc.identifier.scopusauthoridKe, Z=14048262500en_US
dc.identifier.scopusauthoridZhao, C=7403563836en_US
dc.identifier.scopusauthoridGeng, ZY=7101959602en_US
dc.identifier.scopusauthoridWang, YC=10139015200en_US
dc.identifier.scopusauthoridPhillips, DL=7404519365en_US

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