Iron-catalyzed halogenation of alkanes: modeling of nonheme halogenases by experiment and DFT calculations
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 H2O2, tBuOOH, or iodosylbenzene, the high-valent FeO complex efficiently oxidizes and halogenates cyclohexane....
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| Main Authors: | , |
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| Format: | Article (Journal) |
| Language: | English |
| Published: |
May 10, 2010
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| In: |
Chemistry - a European journal
Year: 2010, Volume: 16, Issue: 24, Pages: 7293-7299 |
| ISSN: | 1521-3765 |
| DOI: | 10.1002/chem.201000092 |
| Online Access: | Verlag, lizenzpflichtig, Volltext: https://doi.org/10.1002/chem.201000092 Verlag, lizenzpflichtig, Volltext: https://onlinelibrary.wiley.com/doi/abs/10.1002/chem.201000092 
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| Author Notes: | Peter Comba and Steffen Wunderlich |
| Summary: | 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 H2O2, tBuOOH, or iodosylbenzene, the high-valent FeO 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 CH 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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| Item Description: | Gesehen am 26.05.2023 |
| Physical Description: | Online Resource |
| ISSN: | 1521-3765 |
| DOI: | 10.1002/chem.201000092 |