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11 (not shown) are involved in these reactions cannot be excluded at the present time.
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Very recent results from the Newcomb laboratory have suggested that this species is not a true intermediate but, at least in the case of certain cyclopropylcarbinyl radicals, behaves as "a component of a reacting ensemble" with a very short lifetime of ca. 70 fs: Newcomb, M.; Letadicbiadetti, F. H.; Chestney, D. L.; Roberts, E. S.; Hollenberg, P. F. J. Am. Chem. Soc. 1995, 117, 12085.
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8944228821
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The magnitude of the primary deuterium isotope effect at C-9 must be regarded as a lower limit for the "intrinsic" kinetic isotope effect since our value is derived via an intermolecular competition experiment and is therefore subject to partial masking by other enzymic steps. Large "intrinsic" primary deuterium isotope effects are not uncommon for biological hydrocarbon activations thought to involve iron-oxo species. Cf. ref 16.
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