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Deuterium Kinetic Isotope Effects in Gas-Phase SN2 and E2 Reactions: Comparison of Experiment and Theory
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Section:Abstract
The competition between bimolecular nucleophilc substitution and base-induced elimination is investigated through kinetic isotope effect measurements for gas-phase reactions of RCl + ClO- (R = methyl, ethyl, isopropyl, and tert-butyl) utilizing a FA-SIFT instrument. The overall reaction rate constants and the kinetic isotope effect for the reaction of C2H5Cl + ClO- are compared to computational results. [Hu, W. P.; Truhlar, D. G. J. Am. Chem. Soc. 1996, 118, 860.] Experimental results show that as the degree of substitution in the neutral reactant increases the E2 channel becomes dominant. The systematic change in the overall kinetic isotope effects indicates that, for the reaction of ClO- with C2H5Cl, both the SN2 and E2 pathways do occur, as predicted by computation; however the experimental reaction rate constants and KIE deviate strongly from the computational result.
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This article has been cited by 8 ACS Journal articles (5 most recent appear below).
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Reactions of α-Nucleophiles with Alkyl Chlorides: Competition between SN2 and E2 Mechanisms and the Gas-Phase α-Effect
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Exploring the Reactivity Trends in the E2 and SN2 Reactions of X− + CH3CH2Cl (X = F, Cl, Br, HO, HS, HSe, NH2 PH2, AsH2, CH3, SiH3, and GeH3)
Xiao-Peng Wu, Xiao-Ming Sun, Xi-Guang Wei, Yi Ren, Ning-Bew Wong and Wai-Kee LiJournal of Chemical Theory and Computation2009 5 (6), 1597-1606Exploring the Reactivity Trends in the E2 and SN2 Reactions of X− + CH3CH2Cl (X = F, Cl, Br, HO, HS, HSe, NH2 PH2, AsH2, CH3, SiH3, and GeH3)
Xiao-Peng Wu, Xiao-Ming Sun, Xi-Guang Wei, Yi Ren, Ning-Bew Wong and Wai-Kee LiJournal of Chemical Theory and Computation2009 5 (6), 1597-1606The reactivity order of 12 anions toward ethyl chloride has been investigated by using the G2(+) method, and the competitive E2 and SN2 reactions are discussed and compared. The reactions studied are X− + CH3CH2Cl → HX + CH2═CH2 + Cl− and X− + CH3CH2Cl → ...
A DFT Study of the Kinetic Isotope Effects on the Competing SN2 and E2 Reactions between Hypochlorite Anion and Ethyl Chloride
Anna Pabis, Piotr Paluch, Joanna Szala and Piotr PanethJournal of Chemical Theory and Computation2009 5 (1), 33-36A DFT Study of the Kinetic Isotope Effects on the Competing SN2 and E2 Reactions between Hypochlorite Anion and Ethyl Chloride
Anna Pabis, Piotr Paluch, Joanna Szala and Piotr PanethJournal of Chemical Theory and Computation2009 5 (1), 33-36Kinetic isotope effects (KIEs) on the two alternative reactions, SN2 and E2, between hypochlorite anion and ethyl chloride in water have been studied theoretically using B3LYP and M06−2X functionals. It has been found that the latter one yields more ...
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History
- Published In Issue January 25, 2006
- Received November 2, 2005
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