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Evidence for an Alternative to the Oxygen Rebound Mechanism in C-H Bond Activation by Nonheme FeIVO Complexes.

著者 Cho KB , Wu X , Lee YM , Kwon YH , Shaik S , Nam W
J Am Chem Soc.2012 Dec 3 ; ():.
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The hydroxylation of alkanes by heme FeIVO species occurs via the hydrogen abstraction-oxygen rebound mechanism. It has been assumed that nonheme FeIVO species follow the heme FeIVO paradigm in the C-H bond activation reactions. Herein, we report theoretical and experimental evidence that C-H bond activation of alkanes by synthetic nonheme FeIVO complexes follows an alternative mechanism. Theoretical calculations predict that dissociation of the substrate radical, which is formed past hydrogen abstraction from the alkane, is more favorable than the oxygen rebound or desaturation processes. This theoretical prediction is verified by experimental results that are obtained by analyzing iron and organic products formed in the C-H bond activation of substrates by nonheme FeIVO complexes. The different behavior between heme and nonheme FeIVO species is ascribed to differences in structural preference and exchange enhanced reactivity. Thus, the general consensus that the C-H bond activation by high-valent metal-oxo species, including nonheme FeIVO, occurs via the conventional hydrogen abstraction-oxygen rebound mechanism should be viewed with caution.
PMID: 23205855 [PubMed - as supplied by publisher]
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