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Article: Density functional theory investigation of the remarkable reactivity of geminal dizinc carbenoids (RZn)2CHI(R = Et or I) as cyclopropanation reagents with olefins compared to mono zinc carbenoids RZnCHI2, EtCHIZnR(R = Et or I)

TitleDensity functional theory investigation of the remarkable reactivity of geminal dizinc carbenoids (RZn)2CHI(R = Et or I) as cyclopropanation reagents with olefins compared to mono zinc carbenoids RZnCHI2, EtCHIZnR(R = Et or I)
Authors
Issue Date2002
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, 2002, v. 124 n. 43, p. 12903-12914 How to Cite?
AbstractDensity functional theory calculations for the cyclopropanation reactions of several mono zinc carbenoids and their corresponding gem-dizinc carbenoids with ethylene are reported. The mono zinc carbenoids react with ethylene via an asynchronous attack on one CH 2 group of ethylene with a relatively high barrier to reaction in the 20-25 kcal/mol range similar to other Simmons-Smith type carbenoids previously studied. In contrast, the gem-dizinc carbenoids react with ethylene via a synchronous attack on both CH 2 groups of ethylene and substantially lower barriers to reaction (about 15 kcal/mol) compared to their corresponding mono zinc carbenoid. Both mono zinc and gem-dizinc carbenoid reactions can be accelerated by the addition of Znl 2 groups as a Lewis acid, and this lowers the barrier by another 1.0-5.1 kcal/mol and 0.0-5.5 kcal/mol, respectively, for addition of one Znl 2 group. Our results indicate that gem-dizinc carbenoids react with C=C bonds with significantly lower barriers to reaction and in a noticeably different manner than Simmons-Smith type mono zinc carbenoids. The three gem-dizinc carbenoids have a substantially larger positive charge distribution than those in the mono zinc carbenoids and, hence, a stronger electrophilic character for the germ-dizinc carbenoids.
Persistent Identifierhttp://hdl.handle.net/10722/167774
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.accessioned2012-10-08T03:11:22Z-
dc.date.available2012-10-08T03:11:22Z-
dc.date.issued2002en_US
dc.identifier.citationJournal Of The American Chemical Society, 2002, v. 124 n. 43, p. 12903-12914en_US
dc.identifier.issn0002-7863en_US
dc.identifier.urihttp://hdl.handle.net/10722/167774-
dc.description.abstractDensity functional theory calculations for the cyclopropanation reactions of several mono zinc carbenoids and their corresponding gem-dizinc carbenoids with ethylene are reported. The mono zinc carbenoids react with ethylene via an asynchronous attack on one CH 2 group of ethylene with a relatively high barrier to reaction in the 20-25 kcal/mol range similar to other Simmons-Smith type carbenoids previously studied. In contrast, the gem-dizinc carbenoids react with ethylene via a synchronous attack on both CH 2 groups of ethylene and substantially lower barriers to reaction (about 15 kcal/mol) compared to their corresponding mono zinc carbenoid. Both mono zinc and gem-dizinc carbenoid reactions can be accelerated by the addition of Znl 2 groups as a Lewis acid, and this lowers the barrier by another 1.0-5.1 kcal/mol and 0.0-5.5 kcal/mol, respectively, for addition of one Znl 2 group. Our results indicate that gem-dizinc carbenoids react with C=C bonds with significantly lower barriers to reaction and in a noticeably different manner than Simmons-Smith type mono zinc carbenoids. The three gem-dizinc carbenoids have a substantially larger positive charge distribution than those in the mono zinc carbenoids and, hence, a stronger electrophilic character for the germ-dizinc carbenoids.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.subject.meshCyclopropanes - Chemistryen_US
dc.subject.meshEthylenes - Chemistryen_US
dc.subject.meshModels, Molecularen_US
dc.subject.meshMolecular Conformationen_US
dc.subject.meshOrganometallic Compounds - Chemistryen_US
dc.subject.meshThermodynamicsen_US
dc.subject.meshZinc - Chemistryen_US
dc.titleDensity functional theory investigation of the remarkable reactivity of geminal dizinc carbenoids (RZn)2CHI(R = Et or I) as cyclopropanation reagents with olefins compared to mono zinc carbenoids RZnCHI2, EtCHIZnR(R = Et or I)en_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/ja020965den_US
dc.identifier.pmid12392439-
dc.identifier.scopuseid_2-s2.0-0037202196en_US
dc.identifier.hkuros77150-
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-0037202196&selection=ref&src=s&origin=recordpageen_US
dc.identifier.volume124en_US
dc.identifier.issue43en_US
dc.identifier.spage12903en_US
dc.identifier.epage12914en_US
dc.identifier.isiWOS:000178792400049-
dc.publisher.placeUnited Statesen_US
dc.identifier.scopusauthoridZhao, C=7403563836en_US
dc.identifier.scopusauthoridWang, D=8785092500en_US
dc.identifier.scopusauthoridPhillips, DL=7404519365en_US

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