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• W2755366472 abstract "Abstract The iron(II) triflate complex ( 1 ) of 1,2‐bis(2,2′‐bipyridyl‐6‐yl)ethane, with two bipyridine moieties connected by an ethane bridge, was prepared. Addition of aqueous 30 % H 2 O 2 to an acetonitrile solution of 1 yielded 2 , a green compound with λ max =710 nm. Moessbauer measurements on 2 showed a doublet with an isomer shift (δ) of 0.35 mm/s and a quadrupole splitting (Δ E Q ) of 0.86 mm/s, indicative of an antiferromagnetically coupled diferric complex. Resonance Raman spectra showed peaks at 883, 556 and 451 cm −1 that downshifted to 832, 540 and 441 cm −1 when 1 was treated with H 2 18 O 2 . All the spectroscopic data support the initial formation of a (μ‐hydroxo)(μ‐1,2‐peroxo)diiron(III) complex that oxidizes carbon‐hydrogen bonds. At 0 °C 2 reacted with cyclohexene to yield allylic oxidation products but not epoxide. Weak benzylic C−H bonds of alkylarenes were also oxidized. A plot of the logarithms of the second order rate constants versus the bond dissociation energies of the cleaved C−H bond showed an excellent linear correlation. Along with the observation that oxidation of the probe substrate 2,2‐dimethyl‐1‐phenylpropan‐1‐ol yielded the corresponding ketone but no benzaldehyde, and the kinetic isotope effect, k H /k D , of 2.8 found for the oxidation of xanthene, the results support the hypothesis for a metal‐based H‐atom abstraction mechanism. Complex 2 is a rare example of a (μ‐hydroxo)(μ‐1,2‐peroxo)diiron(III) complex that can elicit the oxidation of carbon‐hydrogen bonds." @default.
• W2755366472 created "2017-09-25" @default.
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• W2755366472 date "2017-09-13" @default.
• W2755366472 modified "2023-10-16" @default.
• W2755366472 title "Hydrogen-Atom Transfer Oxidation with H2 O2 Catalyzed by [FeII(1,2-bis(2,2′-bipyridyl-6-yl)ethane(H2 O)2 ]2+ : Likely Involvement of a (μ-Hydroxo)(μ-1,2-peroxo)diiron(III) Intermediate" @default.
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• W2755366472 doi "https://doi.org/10.1002/ijch.201700059" @default.
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