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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. http://resolver.caltech.edu/CaltechAUTHORS:20170705-095520227

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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.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1002/chem.201702302DOIArticle
http://onlinelibrary.wiley.com/doi/10.1002/chem.201702302/abstractPublisherArticle
https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5659184PubMed CentralArticle
ORCID:
AuthorORCID
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.
Funders:
Funding AgencyGrant Number
NIHR01-GM102687B
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
PubMed Central ID:PMC5659184
Record Number:CaltechAUTHORS:20170705-095520227
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20170705-095520227
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
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:06 Jul 2017 21:55
Last Modified:31 Oct 2017 16:55

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