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Free, publicly-accessible full text available June 26, 2025
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Free, publicly-accessible full text available June 26, 2025
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Oxidation of distorted square-planar perfluoropinacolate Co compound [Co II (pin F ) 2 ] 2− , 1 , to [Co III (pin F ) 2 ] 1− , 2 , is reported. Rigidly square-planar 2 has an intermediate-spin, S = 1, ground state and very large zero-field splitting (ZFS) with D = 67.2 cm −1 ; | E | = 18.0 cm −1 , ( E / D = 0.27), g ⊥ = 2.10, g ‖ = 2.25 and χ TIP = 1950 × 10 −6 cm 3 mol −1 . This Co( iii ) species, 2 , reacts with ROS to oxidise two (pin F ) 2− ligands to form tetrahedral [Co II (Hpfa) 4 ] 2− , 3 .more » « less
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Abstract Oxoiron(IV) units are often implicated as intermediates in the catalytic cycles of non‐heme iron oxygenases and oxidases. The most reactive synthetic analogues of these intermediates are supported by tetradentate tripodal ligands with
N ‐methylbenzimidazole or quinoline donors, but their instability precludes structural characterization. Herein we report crystal structures of two [FeIV(O)(L)]2+complexes supported by pentadentate ligands incorporating these heterocycles, which show longer average Fe–N distances than the complex with only pyridine donors. These longer distances correlate linearly with logk 2′ values for O‐ and H‐atom transfer rates, suggesting that weakening the ligand field increases the electrophilicity of the Fe=O center. The sterically bulkier quinoline donors are also found to tilt the Fe=O unit away from a linear N‐Fe=O arrangement by 10°.