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Selectivity of C-H versus C-F Bond Oxygenation by Homo- and Heterometallic Fe₄ , Fe₃ Mn, and Mn₄ Clusters.

ABSTRACT: A series of tetranuclear [LM₃ (HFArPz)₃ OM'][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.

SUBMITTER: de Ruiter G

PROVIDER: S-EPMC5659184 | biostudies-literature | 2017 Aug

REPOSITORIES: biostudies-literature

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Selectivity of C-H versus C-F Bond Oxygenation by Homo- and Heterometallic Fe4 , Fe3 Mn, and Mn4 Clusters.

de Ruiter Graham G Carsch Kurtis M KM Takase Michael K MK Agapie Theodor T

Chemistry (Weinheim an der Bergstrasse, Germany) 20170724 45

A series of tetranuclear [LM3 (HFArPz)3 OM'][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 invest ...[more]

PMID: 28658508

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