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AbstractAbstract
[en] This paper reports that values of the 14N/15N rate constant ratio for methyl transfer to alkyl-substituted pyridines decrease (become more inverse) as CH3X becomes more reactive and may also decrease as the pyridine becomes more reactive. These changes in K14/K15 demonstrate increasing selectivity for 15N in preference to 14N as reactivity increases and thus are in violation of the reactivity-selectivity principle. However, these observed changes in K14/K15 are consistent with a very recent prediction that such ''anti-Hammond'' effects should result from changes in quantum mechanical mixing of configurations in the transition state and should dominate the more familiar effects of structural perturbations of the free energy surface
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Published in summary form only.
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Journal Article
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Journal of the American Chemical Society; ISSN 0002-7863;
; v. 104(21); p. 5823-5824
; v. 104(21); p. 5823-5824
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