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A computational study of the effect of bending on secondary kinetic isotope effects in SN2 transition states

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dc.contributor.author Hasanayn F.
dc.contributor.author Streitwieser A.
dc.contributor.author Al-Rifai R.
dc.contributor.editor
dc.date 2005
dc.date.accessioned 2017-10-03T15:45:23Z
dc.date.available 2017-10-03T15:45:23Z
dc.date.issued 2005
dc.identifier 10.1021/ja0487978
dc.identifier.isbn
dc.identifier.issn 00027863
dc.identifier.uri http://hdl.handle.net/10938/12621
dc.description.abstract Using conventional transition state theory, the secondary deuterium kinetic isotope effect (KIE) in the inversion SN2 reaction of CH 3F and F- is calculated to be small, 0.98 (T = 298 K). This is shown to be the result of a balance among opposing entropy and enthalpy terms. By contrast, KIE in the retention SN2 mechanism is calculated to be large (1.5). Accordingly, KIE is a potential observable for discriminating between the two mechanisms. Large KIE's are also found for the inversion and retention mechanisms of the ion pair reactions between CH3F and LiF. All of the transition structures leading to large KIE's have a bent FCF angle and an imaginary frequency that is sensitive to deuterium labeling.
dc.format.extent
dc.format.extent Pages: (2249-2255)
dc.language English
dc.publisher WASHINGTON
dc.relation.ispartof Publication Name: Journal of the American Chemical Society; Publication Year: 2005; Volume: 127; no. 7; Pages: (2249-2255);
dc.relation.ispartofseries
dc.relation.uri
dc.source Scopus
dc.subject.other
dc.title A computational study of the effect of bending on secondary kinetic isotope effects in SN2 transition states
dc.type Article
dc.contributor.affiliation Hasanayn, F., Department of Chemistry, American University of Beirut, Beirut, Lebanon
dc.contributor.affiliation Streitwieser, A., Department of Chemistry, University of California, Berkeley, CA 94720-1460, United States
dc.contributor.affiliation Al-Rifai, R., Department of Chemistry, American University of Beirut, Beirut, Lebanon
dc.contributor.authorAddress Hasanayn, F.; Department of Chemistry, American University of Beirut, Beirut, Lebanon; email: fh19@aub.edu.lb
dc.contributor.authorCorporate University: American University of Beirut; Faculty: Faculty of Arts and Sciences; Department: Chemistry;
dc.contributor.authorDepartment Chemistry
dc.contributor.authorDivision
dc.contributor.authorEmail fh19@aub.edu.lb; astreit@berkeley.edu
dc.contributor.faculty Faculty of Arts and Sciences
dc.contributor.authorInitials Hasanayn, F
dc.contributor.authorInitials Streitwieser, A
dc.contributor.authorInitials Al-Rifai, R
dc.contributor.authorOrcidID
dc.contributor.authorReprintAddress Hasanayn, F (reprint author), Amer Univ Beirut, Dept Chem, Beirut, Lebanon.
dc.contributor.authorResearcherID
dc.contributor.authorUniversity American University of Beirut
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dc.description.citedCount 20
dc.description.citedTotWOSCount 20
dc.description.citedWOSCount 20
dc.format.extentCount 7
dc.identifier.articleNo
dc.identifier.coden JACSA
dc.identifier.pubmedID
dc.identifier.scopusID 13944274816
dc.identifier.url
dc.publisher.address 1155 16TH ST, NW, WASHINGTON, DC 20036 USA
dc.relation.ispartofConference
dc.relation.ispartofConferenceCode
dc.relation.ispartofConferenceDate
dc.relation.ispartofConferenceHosting
dc.relation.ispartofConferenceLoc
dc.relation.ispartofConferenceSponsor
dc.relation.ispartofConferenceTitle
dc.relation.ispartofFundingAgency
dc.relation.ispartOfISOAbbr J. Am. Chem. Soc.
dc.relation.ispartOfIssue 7
dc.relation.ispartOfPart
dc.relation.ispartofPubTitle Journal of the American Chemical Society
dc.relation.ispartofPubTitleAbbr J. Am. Chem. Soc.
dc.relation.ispartOfSpecialIssue
dc.relation.ispartOfSuppl
dc.relation.ispartOfVolume 127
dc.source.ID WOS:000227099400045
dc.type.publication Journal
dc.subject.otherAuthKeyword
dc.subject.otherChemCAS deuterium, 7782-39-0
dc.subject.otherIndex Bending (deformation)
dc.subject.otherIndex Enthalpy
dc.subject.otherIndex Entropy
dc.subject.otherIndex Reaction kinetics
dc.subject.otherIndex Ion pair reactions
dc.subject.otherIndex Kinetic isotope effect (KIE)
dc.subject.otherIndex Retention mechanisms
dc.subject.otherIndex Transition state theory
dc.subject.otherIndex Deuterium
dc.subject.otherIndex deuterium
dc.subject.otherIndex isotope
dc.subject.otherIndex article
dc.subject.otherIndex chemical reaction
dc.subject.otherIndex enthalpy
dc.subject.otherIndex entropy
dc.subject.otherIndex isotope labeling
dc.subject.otherIndex kinetics
dc.subject.otherIndex molecular interaction
dc.subject.otherIndex theory
dc.subject.otherKeywordPlus GAS-PHASE REACTIONS
dc.subject.otherKeywordPlus SN2 REACTION
dc.subject.otherKeywordPlus AB-INITIO
dc.subject.otherKeywordPlus LITHIUM ENOLATE
dc.subject.otherKeywordPlus NUCLEOPHILIC-SUBSTITUTION
dc.subject.otherKeywordPlus TEMPERATURE-DEPENDENCE
dc.subject.otherKeywordPlus RETENTION MECHANISMS
dc.subject.otherKeywordPlus ALPHA-DEUTERIUM
dc.subject.otherKeywordPlus DIRECT DYNAMICS
dc.subject.otherKeywordPlus DENSITY
dc.subject.otherWOS Chemistry, Multidisciplinary


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