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The Proton in Chemistry pp 250–296Cite as

Kinetic Isotope Effects in Proton-Transfer Reactions

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Abstract

Kinetic isotope effects in general have now become an everyday tool of the mechanistic organic chemist, and this is particularly true of hydrogen isotope effects, partly because hydrogen is involved in so many reactions, and partly because such effects are much larger for hydrogen than for the isotopes of heavier atoms. It is interesting to note that the rate differences between hydrogen and deuterium compounds are sometimes so large that the use of deuterium compounds has been proposed as a practical expedient for slowing down harmful reactions, e.g., the deterioration of lubricants by oxidation.1 Since the publication of the first edition of this book a number of books and review articles have appeared on the general subject of kinetic isotope effects.2–5 The present chapter will therefore be confined almost entirely to isotope effects in proton-transfer reactions, though some reference will be made to the closely allied problem of reactions involving the transfer of hydrogen atoms, especially in connection with the tunnel effect. On the other hand, no reference will be made to the increasing use of secondary hydrogen isotope effects for obtaining information about neighbouring group participation, especially in solvolytic reactions,6 since these do not normally involve proton transfers. Even in the field of proton-transfer reactions only a selection of the available material has been covered.

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    R. P. Bell (Professor of Chemistry)

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Bell, R.P. (1973). Kinetic Isotope Effects in Proton-Transfer Reactions. In: The Proton in Chemistry. Springer, Boston, MA. https://doi.org/10.1007/978-1-4757-1592-7_12

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