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The magnitude of the isotope effects is similar for hydron transfer from the hydronium ion and from the carboxylic acids, which implies a more symmetrical transition state for the former than for the latter. However experimental data show much more variation in reactivity within the carboxylic acid set than between it and the hydronium ion. As one of the referees suggests this anomaly could be rationalised by considering that isotope effects between electronegative atoms are always secondary with no primary component [see (a)]. Nevertheless the secondary isotope effect of 1.25, which is obtained for denitrosation by carboxylic acid by using the fractionation factors [see (b)], is not consistent with experimental data. We think that the similarity in reactivity between carboxylic acids and the hydronium ion is due to the switch from a neutral to a cationic acid as is reported in the following references. (a) C. G. Swain, D. A. Kuhn and R. L. Schowen, J. Am. Chem. Soc., 1965, 87, 1553; (b) K. B. J. Schowen, in Transition States of Biochemical Processes, eds. R. D. Gandour and R. L. Schowen, Plenum Press, New York, 1978, ch. 6.
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31
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eds. R. D. Gandour and R. L. Schowen, Plenum Press, New York, ch. 6
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The magnitude of the isotope effects is similar for hydron transfer from the hydronium ion and from the carboxylic acids, which implies a more symmetrical transition state for the former than for the latter. However experimental data show much more variation in reactivity within the carboxylic acid set than between it and the hydronium ion. As one of the referees suggests this anomaly could be rationalised by considering that isotope effects between electronegative atoms are always secondary with no primary component [see (a)]. Nevertheless the secondary isotope effect of 1.25, which is obtained for denitrosation by carboxylic acid by using the fractionation factors [see (b)], is not consistent with experimental data. We think that the similarity in reactivity between carboxylic acids and the hydronium ion is due to the switch from a neutral to a cationic acid as is reported in the following references. (a) C. G. Swain, D. A. Kuhn and R. L. Schowen, J. Am. Chem. Soc., 1965, 87, 1553; (b) K. B. J. Schowen, in Transition States of Biochemical Processes, eds. R. D. Gandour and R. L. Schowen, Plenum Press, New York, 1978, ch. 6.
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Transition States of Biochemical Processes
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Schowen, K.B.J.1
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Hopkins, A.R.1
Day, R.A.2
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J. Shakes, C. Raymond, D. Rettura and A. Williams, J. Chem. Soc., Perkin Trans. 2, 1996, 1553.
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Shakes, J.1
Raymond, C.2
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Williams, A.4
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