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• W2068518744 abstract "Abstract An iron(III)–catecholate complex [L 1 Fe III (DBC)] ( 2 ) and an iron(II)– o ‐aminophenolate complex [L 1 Fe II (HAP)] ( 3 ; where L 1 =tris(2‐pyridylthio)methanido anion, DBC=dianionic 3,5‐di‐ tert ‐butylcatecholate, and HAP=monoanionic 4,6‐di‐ tert ‐butyl‐2‐aminophenolate) have been synthesised from an iron(II)–acetonitrile complex [L 1 Fe II (CH 3 CN) 2 ](ClO 4 ) ( 1 ). Complex 2 reacts with dioxygen to oxidatively cleave the aromatic CC bond of DBC giving rise to selective extradiol cleavage products. Controlled chemical or electrochemical oxidation of 2 , on the other hand, forms an iron(III)–semiquinone radical complex [L 1 Fe III (SQ)](PF 6 ) ( 2 ox ‐PF 6 ; SQ=3,5‐di‐ tert ‐butylsemiquinonate). The iron(II)– o ‐aminophenolate complex ( 3 ) reacts with dioxygen to afford an iron(III)– o ‐iminosemiquinonato radical complex [L 1 Fe III (ISQ)](ClO 4 ) ( 3 ox ‐ClO 4 ; ISQ=4,6‐di‐ tert ‐butyl‐ o ‐iminobenzosemiquinonato radical) via an iron(III)– o ‐amidophenolate intermediate species. Structural characterisations of 1 , 2 , 2 ox and 3 ox reveal the presence of a strong ironcarbon bonding interaction in all the complexes. The bond parameters of 2 ox and 3 ox clearly establish the radical nature of catecholate‐ and o ‐aminophenolate‐derived ligand, respectively. The effect of ironcarbon bonding interaction on the dioxygen reactivity of biomimetic iron–catecholate and iron– o ‐aminophenolate complexes is discussed." @default.
• W2068518744 created "2016-06-24" @default.
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• W2068518744 date "2012-07-29" @default.
• W2068518744 modified "2023-10-18" @default.
• W2068518744 title "Dioxygen Reactivity of Biomimetic Iron-Catecholate and Iron-<i>o</i>-Aminophenolate Complexes of a Tris(2-pyridylthio)methanido Ligand: Aromatic CC Bond Cleavage of Catecholate versus<i>o</i>-Iminobenzosemiquinonate Radical Formation" @default.
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• W2068518744 doi "https://doi.org/10.1002/chem.201200886" @default.
• W2068518744 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/22847897" @default.
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