1 Ocak 2016 Dergi makalesi Açık Erişim

Degirmenci, Isa; Coote, Michelle L.

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  <identifier identifierType="URL">https://aperta.ulakbim.gov.tr/record/55413</identifier>
  <creators>
    <creator>
      <creatorName>Degirmenci, Isa</creatorName>
      <givenName>Isa</givenName>
      <familyName>Degirmenci</familyName>
    </creator>
    <creator>
      <creatorName>Coote, Michelle L.</creatorName>
      <givenName>Michelle L.</givenName>
      <familyName>Coote</familyName>
      <affiliation>Australian Natl Univ, Res Sch Chem, ARC Ctr Excellence Electromat Sci, GPO Box 4, Canberra, ACT 2601, Australia</affiliation>
    </creator>
  </creators>
  <titles>
    <title>Comparison Of Thiyl, Alkoxyl, And Alkyl Radical Addition To Double Bonds: The Unusual Contrasting Behavior Of Sulfur And Oxygen Radical Chemistry</title>
  </titles>
  <publisher>Aperta</publisher>
  <publicationYear>2016</publicationYear>
  <dates>
    <date dateType="Issued">2016-01-01</date>
  </dates>
  <resourceType resourceTypeGeneral="Text">Journal article</resourceType>
  <alternateIdentifiers>
    <alternateIdentifier alternateIdentifierType="url">https://aperta.ulakbim.gov.tr/record/55413</alternateIdentifier>
  </alternateIdentifiers>
  <relatedIdentifiers>
    <relatedIdentifier relatedIdentifierType="DOI" relationType="IsIdenticalTo">10.1021/acs.jpca.6b00538</relatedIdentifier>
  </relatedIdentifiers>
  <rightsList>
    <rights rightsURI="http://www.opendefinition.org/licenses/cc-by">Creative Commons Attribution</rights>
    <rights rightsURI="info:eu-repo/semantics/openAccess">Open Access</rights>
  </rightsList>
  <descriptions>
    <description descriptionType="Abstract">High-level ab initio calculations have been used to compare prototypical thiyl, alkoxyl, and alkyl radical addition reactions. Thiyl radical addition to the sulfur center of thioketones is exothermic and rapid, occurring with negative enthalpic barriers and only weakly positive Gibbs free energy barriers. In stark contrast, alkoxyl radical addition to the oxygen center of ketones is highly endothermic and occurs with very high reaction barriers, though these are also suppressed. On the basis of analysis of the corresponding alkyl radical additions to these substrates and the corresponding reactions of these heteroatom radicals with alkenes, it suggested that addition reactions involving thiyl radicals have low intrinsic barriers because their unpaired electrons are better able to undergo stabilizing resonance interactions with the pi* orbitals of the substrate in the transition state.</description>
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