Selectivity of C−H vs. C−F Bond Oxygenation by Homo- and Heterometallic Fe_4, Fe_3Mn, and Mn_4 Clusters
Abstract
A series of tetranuclear [LM_3(HFArPz)_3OM'][OTf]_2 (M, M' = Fe or Mn) clusters that displays 3-(2-fluorophenyl)pyrazolate (HFArPz) as bridging ligand is reported. With these complexes manganese is demonstrated to facilitate C(sp^2)−F bond oxygenation via a putative terminal metal-oxo species. Moreover, the presence of both ortho C(sp^2)−H and C(sp^2)−F bonds in proximity provides an opportunity to investigate the selectivity of intramolecular C(sp^2)−X bond oxygenation (X = H or F) in these isostructural compounds. With iron as the apical metal center (M' = Fe) C(sp^2)−F bond oxygenation occurs almost exclusively, whereas with manganese (M' = Mn) the opposite reactivity is preferred.
Additional Information
© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. Manuscript received: May 19, 2017; Accepted manuscript online: June 28, 2017; Version of record online: July 24, 2017. This research was supported by the NIH (R01-GM102687B). T.A. is grateful for a Dreyfus fellowship. K.M.C. is grateful for a Summer Undergraduate Research Fellowship. We thank Lawrence M. Henling for assistance with X-ray crystallography. We would also like to thank Mona Shahgholi for assistance with mass spectrometry.Attached Files
Accepted Version - Ruiter_et_al-2017-Chemistry_-_A_European_Journal.pdf
Accepted Version - nihms913583.pdf
Supplemental Material - chem201702302-sup-0001-SI1.pdf
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Additional details
- Alternative title
- Selectivity of C−H vs. C−F Bond Oxygenation by Homo- and Heterometallic Fe4, Fe3Mn, and Mn4 Clusters
- PMCID
- PMC5659184
- Eprint ID
- 78757
- Resolver ID
- CaltechAUTHORS:20170705-095520227
- R01-GM102687B
- NIH
- Camille and Henry Dreyfus Foundation
- Caltech Summer Undergraduate Research Fellowship (SURF)
- Created
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2017-07-06Created from EPrint's datestamp field
- Updated
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2022-03-23Created from EPrint's last_modified field