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Selectivity of C−H versus C−F Bond Oxygenation by Homo‐ and Heterometallic Fe 4 , Fe 3 Mn, and Mn 4 Clusters
Author(s) -
de Ruiter Graham,
Carsch Kurtis M.,
Takase Michael K.,
Agapie Theodor
Publication year - 2017
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201702302
Subject(s) - isostructural , manganese , crystallography , metal , chemistry , intramolecular force , ligand (biochemistry) , reactivity (psychology) , selectivity , center (category theory) , bond length , stereochemistry , crystal structure , catalysis , medicine , biochemistry , receptor , alternative medicine , organic chemistry , pathology
A series of tetranuclear [LM 3 (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(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 of the apical metal center provided 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 occur almost exclusively, whereas with manganese (M′=Mn), the opposite reactivity is preferred.