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note
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Because of the assumptions made in calculating the isotope effects, we have made no attempt to correlate the magnitude of the isotope effect with the structure of the transition state. The critical feature of the calculated effects is that formation of I should result in an inverse isotope effect only upon deuteration of carbon 5, while formation of II will result in inverse effects upon deuteration at either position. Thus, it is the relative magnitudes of the effects at the two positions which is diagnostic of mechanism. The values measured with 295 μM oxygen are clearly not the intrinsic effects, as demonstrated by the more inverse effect seen at 830 μM oxygen.
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