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

Show simple item record Hasanayn F. Streitwieser A. Al-Rifai R.
dc.contributor.editor 2005 2017-10-03T15:45:23Z 2017-10-03T15:45:23Z 2005
dc.identifier 10.1021/ja0487978
dc.identifier.issn 00027863
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 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.source Scopus
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:
dc.contributor.authorCorporate University: American University of Beirut; Faculty: Faculty of Arts and Sciences; Department: Chemistry;
dc.contributor.authorDepartment Chemistry
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.authorReprintAddress Hasanayn, F (reprint author), Amer Univ Beirut, Dept Chem, Beirut, Lebanon.
dc.contributor.authorUniversity American University of Beirut
dc.description.cited Abu-Hasanayn F, 1998, J ORG CHEM, V63, P2954, DOI 10.1021-jo972128d; Albu TV, 2002, J PHYS CHEM A, V106, P5323, DOI 10.1021-jp020544i; Alhambra C, 1999, J AM CHEM SOC, V121, P2253, DOI 10.1021-ja9831655; BECKE AD, 1993, J CHEM PHYS, V98, P5648, DOI 10.1063-1.464913; BIEGELEISEN J, 1949, J CHEM PHYS, V17, P675; BIEGELEISEN J, 1947, J CHEM PHYS, V15, P261; Carpenter B. K., 1984, DETERMINATION ORGANI; CRAMER CJ, 2002, ESSENTIALS COMPUTATO; Davico GE, 2000, J AM CHEM SOC, V122, P1740, DOI 10.1021-ja993093x; DePuy CH, 2002, J ORG CHEM, V67, P2393, DOI 10.1021-jo0163593; Fang YR, 2003, CHEM-EUR J, V9, P2696, DOI 10.1002-chem.200204119; Frisch M. J., 2003, GAUSSIAN 03 REVISION; Garcia-Viloca M, 2004, SCIENCE, V303, P186, DOI 10.1126-science.1088172; Glad SS, 1997, J AM CHEM SOC, V119, P227, DOI 10.1021-ja962733i; GONZALEZLAFONT A, 1991, J PHYS CHEM-US, V95, P4618, DOI 10.1021-j100165a009; Griffin TR, 1996, J AM CHEM SOC, V118, P3029, DOI 10.1021-ja952952o; GRONERT S, 1991, J AM CHEM SOC, V113, P4009, DOI 10.1021-ja00010a063; HARDER S, 1995, J AM CHEM SOC, V117, P3253, DOI 10.1021-ja00116a029; AbuHasanayn F, 1996, J AM CHEM SOC, V118, P8136, DOI 10.1021-ja960742l; Hehre W.J., 1986, AB INITIO MOL ORBITA; HU WP, 1994, J AM CHEM SOC, V116, P7797, DOI 10.1021-ja00096a041; Hu WP, 1997, J PHYS CHEM A, V101, P6911, DOI 10.1021-jp970188h; HU WP, 1995, J AM CHEM SOC, V117, P10726, DOI 10.1021-ja00148a015; Laidler K. J., 1987, CHEM KINETICS; LEE CT, 1988, PHYS REV B, V37, P785, DOI 10.1103-PhysRevB.37.785; LU DH, 1990, J AM CHEM SOC, V112, P7504; McQuarrie DA, 1999, MOL THERMODYNAMICS; OHAIR RAJ, 1994, J AM CHEM SOC, V116, P3609, DOI 10.1021-ja00087a061; POIRIER RA, 1994, J AM CHEM SOC, V116, P2526, DOI 10.1021-ja00085a037; Pratt LM, 2003, J ORG CHEM, V68, P2830, DOI 10.1021-jo026902v; Pugh JK, 2001, J ORG CHEM, V66, P1334, DOI 10.1021-jo001286t; Ren Y, 2004, J COMPUT CHEM, V25, P461, DOI 10.1002-jcc.10394; Ruggiero GD, 2002, J CHEM SOC PERK T 2, P591, DOI 10.1039-b108428c; Shaik S. S., 1992, THEORETICAL ASPECTS; STORER JW, 1993, J AM CHEM SOC, V115, P10426, DOI 10.1021-ja00075a095; Streitwieser A, 1997, J AM CHEM SOC, V119, P5013, DOI 10.1021-ja961673d; Sun L, 2001, J AM CHEM SOC, V123, P5753, DOI 10.1021-ja004077z; Tachikawa H, 2002, J PHYS CHEM A, V106, P10977, DOI 10.1021-jp0210632; THANH N, 1991, J AM CHEM SOC, V113, P7504; TRUHLAR DG, 1989, J AM CHEM SOC, V111, P1232, DOI 10.1021-ja00186a010; TRUHLAR DG, 1980, ACCOUNTS CHEM RES, V13, P440, DOI 10.1021-ar50156a002; TRUHLAR DG, 1992, ACS SYM SER, V502, P16; Truhlar DG, 2002, ACCOUNTS CHEM RES, V35, P341, DOI 10.1021-ar0100226; TUCKER SC, 1990, J AM CHEM SOC, V112, P3338, DOI 10.1021-ja00165a013; VIGGIANO AA, 1991, J AM CHEM SOC, V113, P9404, DOI 10.1021-ja00024a076; VIGGIANO AA, 1992, J AM CHEM SOC, V114, P10477, DOI 10.1021-ja00052a050; Wang DZ, 1999, THEOR CHEM ACC, V102, P78, DOI 10.1007-s002140050475; Wang YF, 2003, J CHEM PHYS, V118, P2688, DOI 10.1063-1.1535890; ZHAO XG, 1991, J AM CHEM SOC, V113, P826, DOI 10.1021-ja00003a015; ZHAO XG, 1992, J CHEM PHYS, V97, P6369, DOI 10.1063-1.463698
dc.description.citedCount 20
dc.description.citedTotWOSCount 20
dc.description.citedWOSCount 20
dc.format.extentCount 7
dc.identifier.coden JACSA
dc.identifier.scopusID 13944274816
dc.publisher.address 1155 16TH ST, NW, WASHINGTON, DC 20036 USA
dc.relation.ispartOfISOAbbr J. Am. Chem. Soc.
dc.relation.ispartOfIssue 7
dc.relation.ispartofPubTitle Journal of the American Chemical Society
dc.relation.ispartofPubTitleAbbr J. Am. Chem. Soc.
dc.relation.ispartOfVolume 127
dc.source.ID WOS:000227099400045
dc.type.publication Journal
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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