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Gas-phase Reactions Of Anions With Halogenated Methanes At 297 ± 2 K

K. Tanaka, G. Mackay, J. D. Payzant, D. Bohme
Published 1976 · Chemistry

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The rate constants for a number of exothermic displacement (SN2) reactions of the type X− + CH3Y → Y− + CH3X where X− = H−, O−, C−, F−, S−, Cl−, OH−, C2−, CN−, SH−, S2−, C2H−, NH2−, NO2−, CHF−, CH2Cl−, CH2Br−, CH3O−, CH3S−, and CH3NH− and Y = F, Cl, and Br, have been measured in the gas phase at 297 ± 2 K using the flowing after-glow technique. These gas-phase measurements provided an opportunity to determine the intrinsic nucleophilic reactivity of 'nude' anions and hence to assess the role of solvation in the kinetics of SN2 reactions proceeding in solution. Comparisons of the experimental rate constants with rate constants calculated using classical theories of capture indicate that several displacement reactions may possess large intrinsic energies of activation, . Correlations were found between apparent activation energies and the heats of reaction. These correlations provided a convenient classification of the various anion nucleophiles. Displacement was observed to compete with proton transfer in ...



This paper is referenced by
10.1002/QUA.560380214
Theoretical approach to reactions of polyatomic molecules
L. Zülicke (1990)
10.1063/1.478913
Quantum scattering calculations on the SN2 reaction Cl−+CH3Br→ClCH3+Br−
S. Schmatz (1999)
10.1002/JCC.540100204
AM1 studies on the potential energy surface for the proton transfer in protonated water clusters, H+(H2O)n
J. Choi (1989)
10.1016/J.COMPTC.2011.02.005
Geometrical and kinetic isotope effects on SN2 chemical reactions using multi-component molecular orbital method
Yoko Kikuta (2011)
10.1021/AR50147A003
Bimolecular reactions of nucleophiles in the gas phase
J. H. Bowie (1980)
10.1016/0168-1176(95)04245-G
The interplay between electron transfer and attack on halogen in gas-phase reactions of negative ions with fluoro-chloromethanes and fluoro-bromomethanes
P. O. Staneke (1995)
10.1002/POC.610040303
Reactivity in radical abstraction reactions: Application of the curve crossing model
A. Pross (1991)
10.1016/S1387-3806(00)00215-3
Coupled cluster calculations for the SN2 reaction Cl− + CH3Br → ClCH3 + Br−
S. Schmatz (2000)
10.1016/0301-0104(94)87032-2
Dynamical study of competing reactions in the CN−-H2 collisional system by a multicoincident detection
K. Goudjil (1994)
10.1016/0009-2614(84)85006-X
An ab initio MO study on the thiol—disulphide exchange reaction
M. Aida (1984)
10.1139/V07-146
Gaseous ions and chemical mass spectrometry
D. Bohme (2008)
10.1002/cphc.202000039
Hybrid Solvation Model with First Solvation Shell for Calculation of Solvation Free Energy.
Xin Xin (2020)
10.1007/978-3-642-93085-0_7
Mechanistic Studies of Some Gas Phase Reactions of O∙- Ions with Organic Substrates
J. H. Dawson (1978)
10.1016/0168-1176(87)80010-1
Formation of carbene radical anions: gas-phase reaction of the atomic oxygen anion with organic neutrals
J. Grabowski (1987)
10.1063/1.443392
Dynamical polar solvent effects on solution reactions: A simple continuum model
G. Zwan (1982)
10.1016/0009-2614(86)80171-3
Dynamical interpretation of the low efficiency of gas-phase nucleophilic substitution reactions (SN2)
M. V. Basilevsky (1986)
10.1063/1.449910
Vibrationally state‐selected reactions of ammonia ions. II. NH+3(v)+CH4
R. Morrison (1986)
10.1039/A900379G
Nature of the transition state in gas phase SN2 identity reactions: correlation between nucleophilicity and proton affinity
E. Uggerud (1999)
10.1016/J.THEOCHEM.2007.01.037
The study of counterion effect on the reactivity of nucleophiles in some SN2 reactions in gas phase and solvent media
Ali Ebrahimi (2007)
10.1002/RECL.19881070504
The nucleophilic addition-elimination reaction on the carbonyl group of pivaloyl chloride, S-methyl thiopivaloate and 1-pivaloyl-1,2,4-triazole in the gas phase†
H. Wel (2010)
10.1016/J.THEOCHEM.2010.02.008
Static and dynamic reaction pathways involved in the reaction of O− and CH3F
F. Yu (2010)
10.1016/S1872-1508(06)60050-8
Investigation of the Mechanism of the Reaction between Atomic Oxygen Radical Anion and Benzene
Y. Zhao (2006)
10.1016/S0040-4020(98)00773-X
Some difficulties encountered with AM1 and PM3 calculations
Nguyên Trong Anh (1998)
10.1016/S0168-1176(96)04409-6
Selected ion flow tube studies of the gas-phase reactions of O·-, O2·- and OH- with a variety of brominated compounds
R. Thomas (1996)
10.1002/MAS.1280050202
Fourier transform mass spectrometry: Recent instrumental developments and applications
D. Laude (1986)
10.1016/S0166-1280(03)00162-3
Car-parrinello molecular dynamics on the SN2 reaction Cl- + CH3Br in water
M. Pagliai (2003)
10.1016/0168-1176(93)80033-B
Gas phase ionic reactions of freons and related compounds: reactions of some halogenated methanes with O− and O2−
C. Mayhew (1993)
10.1039/c4cp02635g
Solvent effects and potential of mean force: a multilayered-representation quantum mechanical/molecular mechanics study of the CH3Br + CN- reaction in aqueous solution.
Yulong Xu (2014)
10.1002/KIN.550130403
From energy profiles to structure–reactivity correlations
N. Agmon (1981)
10.1021/ja906814d
Uracil and thymine reactivity in the gas phase: the S(N)2 reaction and implications for electron delocalization in leaving groups.
Anna E. Zhachkina (2009)
10.1016/S0040-4020(01)81303-X
Generation, thermochemistry, and chemistry of carbene anion radicals and related species
R. Mcdonald (1989)
10.1007/S11743-011-1300-5
Study of the SN2 Substitution Reactions Between Methyl Naphtalene-2-Sulfonate and Methyl 4-Nitrobenzene Sulfonate and Bromide Ions in Dodecyl Dibromide Dimeric Micellar Solutions in the Absence and Presence of Alcohols
María Mar Graciani (2012)
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