4 years ago

Selectivity of C−H versus C−F Bond Oxygenation by Homo- and Heterometallic Fe4, Fe3Mn, and Mn4 Clusters

Selectivity of C−H versus C−F Bond Oxygenation by Homo- and Heterometallic Fe4, Fe3Mn, and Mn4 Clusters
Theodor Agapie, Graham de Ruiter, Michael K. Takase, Kurtis M. Carsch
A series of tetranuclear [LM3(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 was demonstrated to facilitate C(sp2)−F bond oxygenation via a putative terminal metal-oxo species. Moreover, the presence of both ortho C(sp2)−H and C(sp2)−F bonds in proximity of the apical metal center provided an opportunity to investigate the selectivity of intramolecular C(sp2)−X bond oxygenation (X=H or F) in these isostructural compounds. With iron as the apical metal center, (M′=Fe) C(sp2)−F bond oxygenation occur almost exclusively, whereas with manganese (M′=Mn), the opposite reactivity is preferred. Oxygen atom transfer: The selectivity of intramolecular C(sp2)−H versus C(sp2)−F bond oxygenation was examined with a new series of [LM3(PhPz)3OM′][OTf]2 (M, M′=Fe or Mn) clusters. The distribution of metal centers within these clusters provided insight into how a single metal center (Fe vs. Mn) can control the selectivity of oxygenation chemistry. Although for iron (M=Fe, M′=Fe) essentially exclusive C(sp2)−F bond oxygenation was observed, with manganese (M=Fe or Mn, M′=Mn), C(sp2)−H oxygenation was preferred (see scheme).

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/chem.201702302

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