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Selectivity of C−H vs. C−F Bond Oxygenation by Homo- and Heterometallic Fe_4, Fe_3Mn, and Mn_4 Clusters

De Ruiter, Graham and Carsch, Kurtis M. and Takase, Michael K. and Agapie, Theodor (2017) Selectivity of C−H vs. C−F Bond Oxygenation by Homo- and Heterometallic Fe_4, Fe_3Mn, and Mn_4 Clusters. Chemistry: a European Journal, 23 (45). pp. 10744-10748. ISSN 0947-6539. PMCID PMC5659184.

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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.

Item Type:Article
Related URLs:
URLURL TypeDescription CentralArticle
Carsch, Kurtis M.0000-0003-4432-7518
Takase, Michael K.0000-0001-8365-3645
Agapie, Theodor0000-0002-9692-7614
Alternate Title:Selectivity of C−H vs. C−F Bond Oxygenation by Homo- and Heterometallic Fe4, Fe3Mn, and Mn4 Clusters
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.
Funding AgencyGrant Number
Camille and Henry Dreyfus FoundationUNSPECIFIED
Caltech Summer Undergraduate Research Fellowship (SURF)UNSPECIFIED
Subject Keywords:C-H bond oxygenation; C-F bond oxygenation; multimetallic complexes; oxygen atom transfer; clusters
Issue or Number:45
PubMed Central ID:PMC5659184
Record Number:CaltechAUTHORS:20170705-095520227
Persistent URL:
Official Citation:G. de Ruiter, K. M. Carsch, M. K. Takase, T. Agapie, Chem. Eur. J. 2017, 23, 10744
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:78757
Deposited By: Tony Diaz
Deposited On:06 Jul 2017 21:55
Last Modified:09 Mar 2020 13:19

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