Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 16, Issue 24, Pages 7293-7299Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201000092
Keywords
density functional calculations; enzyme models; halogenation; iron; oxidation
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Funding
- German Science Foundation (DFG)
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When the dichloroiron(II) complex of the tetradentate bispidine ligand L=3,7-dimethyl-9-oxo-2,4-bis(2-pyridyl)-3,7-diazabicyclo[3.3.1]nonane- 1,5-dicarboxylate methyl ester is oxidized with H(2)O(2), tBuOOH, or iodosylbenzene, the high-valent Fe=0 complex efficiently oxidizes and halogenates cyclohexane. Kinetic D isotope effects and the preference for the abstraction of tertiary over secondary carbon-bound hydrogen atoms (quantified in the halogenation of adamantane) indicate that C-H activation is the rate-determining step. The efficiencies (yields in stoichiometric and turnover numbers in catalytic reactions), product ratios (alcohol vs. bromo- vs. chloroalkane), and kinetic isotope effects depend on the oxidant. These results suggest different pathways with different oxidants, and these may include iron(IV)- and iron(V)-oxo complexes as well as oxygen-based radicals.
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