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- Publisher Website: 10.1021/ja020965d
- Scopus: eid_2-s2.0-0037202196
- PMID: 12392439
- WOS: WOS:000178792400049
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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)
Title | 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) |
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Authors | |
Issue Date | 2002 |
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, 2002, v. 124 n. 43, p. 12903-12914 How to Cite? |
Abstract | Density 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 Identifier | http://hdl.handle.net/10722/167774 |
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 | 2012-10-08T03:11:22Z | - |
dc.date.available | 2012-10-08T03:11:22Z | - |
dc.date.issued | 2002 | en_US |
dc.identifier.citation | Journal Of The American Chemical Society, 2002, v. 124 n. 43, p. 12903-12914 | en_US |
dc.identifier.issn | 0002-7863 | en_US |
dc.identifier.uri | http://hdl.handle.net/10722/167774 | - |
dc.description.abstract | Density 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.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.subject.mesh | Cyclopropanes - Chemistry | en_US |
dc.subject.mesh | Ethylenes - Chemistry | en_US |
dc.subject.mesh | Models, Molecular | en_US |
dc.subject.mesh | Molecular Conformation | en_US |
dc.subject.mesh | Organometallic Compounds - Chemistry | en_US |
dc.subject.mesh | Thermodynamics | en_US |
dc.subject.mesh | Zinc - Chemistry | en_US |
dc.title | 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) | 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/ja020965d | en_US |
dc.identifier.pmid | 12392439 | - |
dc.identifier.scopus | eid_2-s2.0-0037202196 | en_US |
dc.identifier.hkuros | 77150 | - |
dc.relation.references | http://www.scopus.com/mlt/select.url?eid=2-s2.0-0037202196&selection=ref&src=s&origin=recordpage | en_US |
dc.identifier.volume | 124 | en_US |
dc.identifier.issue | 43 | en_US |
dc.identifier.spage | 12903 | en_US |
dc.identifier.epage | 12914 | en_US |
dc.identifier.isi | WOS:000178792400049 | - |
dc.publisher.place | United States | en_US |
dc.identifier.scopusauthorid | Zhao, C=7403563836 | en_US |
dc.identifier.scopusauthorid | Wang, D=8785092500 | en_US |
dc.identifier.scopusauthorid | Phillips, DL=7404519365 | en_US |
dc.identifier.issnl | 0002-7863 | - |