Marcus theory and the existence or non-existence of transition states in gas phase deprotonation of carbon acids
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At the 3-21G (3-21G*) computational level, the intrinsic barriers associated with proton transfer between XCH2− and CH3X have been found to be essentially constant (ca. 10 kcal/mol) for X = H, F, SH, Cl. According to the Marcus rate-equilibrium treatment of proton transfer reactions, this result means that transition states should not exist for gas phase reactions [Formula: see text], when the energy change exceeds 20 kcal/mol. This prediction has been confirmed for two cases (X = H, F) in which the energy change is less than 20 kcal/mol, and two cases (X = SH, Cl) in which the energy change is greater than 20 kcal/mol.
2017 ◽
Vol 28
(8)
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pp. 1676-1686
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1992 ◽
Vol 3
(6)
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pp. 624-630
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1979 ◽
Vol 57
(12)
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pp. 1518-1523
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2018 ◽
Vol 122
(43)
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pp. 9947-9955
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1995 ◽
Vol 6
(6)
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pp. 529-532
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