Article: Isopolyhalomethanes: Their formation, structures, properties and cyclopropanation reactions with olefins

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TitleIsopolyhalomethanes: Their formation, structures, properties and cyclopropanation reactions with olefins
AuthorsPhillips, DL2
Fang, WH1
Zheng, X3
Li, YL2
Wang, D2
Kwok, WM2
Issue Date2004
PublisherBentham Science Publishers Ltd. The Journal's web site is located at http://www.bentham.org/coc/index.htm
CitationCurrent Organic Chemistry, 2004, v. 8 n. 9, p. 739-755 [How to Cite?]
DOI: http://dx.doi.org/10.2174/1385272043370483
AbstractAn overview of recent research on isopolyhalomethanes is presented that examines their formation, structure, properties and cyclopropanation reactions with olefins. Time-resolved experimental results show isopolyhalomethanes are formed vibrationally hot within a few picoseconds following solvent induced geminate recombination of the initially produced haloalkyl radical and halogen atom fragments of the parent polyhalomethane molecule photodissociation. The carbenoid behavior of the CH 2I-I isomer toward C=C bonds can be largely attributed to the CH 2I +I - radical ion pair character that activates the CH2 I moiety and the sp 2 bonding character of the C atom in the isopolyhalomethane species. Time-resolved resonance Raman and density functional theory studies on selected isopolyhalomethanes and their cyclopropanation reactions with olefins indicates the isopolyhalomethane lifetime and chemical reactivity relative to the intitially formed haloalkyl radical fragments helps to determine the efficiency of the isopolyhalomethane cyclopropanation reactions. The chemical reactivity of the CH 2I-I and the classic Simmons-Smith IZnCH 2I carbenoids towards olefins can be largely explained by their differing energetics for releasing the leaving group, steric demands and electrophilic character of the methylene group to be transferred. © 2004 Bentham Science Publishers Ltd.
ISSN1385-2728
2011 Impact Factor: 3.064
2011 SCImago Journal Rankings: 0.213
DOIhttp://dx.doi.org/10.2174/1385272043370483
ISI Accession Number IDWOS:000221362200001
ReferencesReferences in Scopus
DC Field
Value
dc.contributor.authorPhillips, DL
dc.contributor.authorFang, WH
dc.contributor.authorZheng, X
dc.contributor.authorLi, YL
dc.contributor.authorWang, D
dc.contributor.authorKwok, WM
dc.date.accessioned2010-09-06T06:23:34Z
dc.date.available2010-09-06T06:23:34Z
dc.date.issued2004
dc.description.abstractAn overview of recent research on isopolyhalomethanes is presented that examines their formation, structure, properties and cyclopropanation reactions with olefins. Time-resolved experimental results show isopolyhalomethanes are formed vibrationally hot within a few picoseconds following solvent induced geminate recombination of the initially produced haloalkyl radical and halogen atom fragments of the parent polyhalomethane molecule photodissociation. The carbenoid behavior of the CH 2I-I isomer toward C=C bonds can be largely attributed to the CH 2I +I - radical ion pair character that activates the CH2 I moiety and the sp 2 bonding character of the C atom in the isopolyhalomethane species. Time-resolved resonance Raman and density functional theory studies on selected isopolyhalomethanes and their cyclopropanation reactions with olefins indicates the isopolyhalomethane lifetime and chemical reactivity relative to the intitially formed haloalkyl radical fragments helps to determine the efficiency of the isopolyhalomethane cyclopropanation reactions. The chemical reactivity of the CH 2I-I and the classic Simmons-Smith IZnCH 2I carbenoids towards olefins can be largely explained by their differing energetics for releasing the leaving group, steric demands and electrophilic character of the methylene group to be transferred. © 2004 Bentham Science Publishers Ltd.
dc.description.natureLink_to_subscribed_fulltext
dc.identifier.citationCurrent Organic Chemistry, 2004, v. 8 n. 9, p. 739-755 [How to Cite?]
DOI: http://dx.doi.org/10.2174/1385272043370483
dc.identifier.doihttp://dx.doi.org/10.2174/1385272043370483
dc.identifier.epage755
dc.identifier.hkuros90651
dc.identifier.isiWOS:000221362200001
dc.identifier.issn1385-2728
2011 Impact Factor: 3.064
2011 SCImago Journal Rankings: 0.213
dc.identifier.issue9
dc.identifier.openurl
dc.identifier.scopuseid_2-s2.0-2442484390
dc.identifier.spage739
dc.identifier.urihttp://hdl.handle.net/10722/70511
dc.identifier.volume8
dc.languageeng
dc.publisherBentham Science Publishers Ltd. The Journal's web site is located at http://www.bentham.org/coc/index.htm
dc.publisher.placeNetherlands
dc.relation.ispartofCurrent Organic Chemistry
dc.relation.referencesReferences in Scopus
dc.titleIsopolyhalomethanes: Their formation, structures, properties and cyclopropanation reactions with olefins
dc.typeArticle
Author Affiliations
  1. Beijing Normal University
  2. The University of Hong Kong
  3. Zhejiang Sci-Tech University