Intramolecular C–H and C–F Bond Oxygenation Mediated by a Putative Terminal Oxo Species in Tetranuclear Iron Complexes
Abstract
Herein we report the intramolecular arene C–H and C–F bond oxygenation by tetranuclear iron complexes. Treatment of [LFe_3(PhPz)_3OFe][OTf]_2 (1) or its fluorinated analog [LFe_3(F2ArPz)_3OFe][OTf]_2 (5) with iodosobenzene results in the regioselective hydroxylation of a bridging pyrazolate ligand, converting a C–H or C–F bond into a C–O bond. The observed reactivity suggests the formation of terminal and reactive Fe-oxo intermediates. With the possibility of intramolecular electron transfer within clusters in 1 and 5, different reaction pathways (Fe^(IV)-oxo vs Fe^(III)-oxo) might be responsible for the observed arene hydroxylation.
Additional Information
© 2016 American Chemical Society. Received: November 22, 2015. Article ASAP. Publication Date (Web): January 13, 2016. This research was supported by the NIH (R01-GM102687A). T.A. is grateful for Sloan, Dreyfus, and Cottrell fellowships. T.A. and G. de R. are grateful for a Camille & Henry Dreyfus Environmental Chemistry Fellowship. We thank Lawrence M. Henling for assistance with crystallography. The authors declare no competing financial interest.Attached Files
Accepted Version - nihms786209.pdf
Supplemental Material - ja5b12214_si_001.cif
Supplemental Material - ja5b12214_si_002.pdf
Files
Additional details
- PMCID
- PMC4871154
- Eprint ID
- 64298
- Resolver ID
- CaltechAUTHORS:20160208-092710615
- R01-GM102687A
- NIH
- Alfred P. Sloan Foundation
- Camille and Henry Dreyfus Foundation
- Cottrell Scholar of Research Corporation
- Created
-
2016-02-08Created from EPrint's datestamp field
- Updated
-
2022-05-12Created from EPrint's last_modified field