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- W2074153552 endingPage "994" @default.
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- W2074153552 abstract "Three new nitrogen-donor ligands with ferrocenyl pendants, namely ferrocenylmethylbis(2-pyridylethyl)amine (L1), ferrocenylmethylbis(2-pyridylmethyl)amine (L2), and 1-ferrocenylmethyl-4,7-diisopropyl-1,4,7-triazacyclononane (L3), have been synthesised. Copper(II) complexes of these ligands have been made and their physicochemical and redox properties characterised. Crystal structures of [Cu(L2)X2·0.5Et2O (X = Cl, Br), [Cu(L2)(OTf)2(CH3OH)], [Cu(L3)Cl2], and [{(L3)Cu}2(μ-OH)2](OTf)2·0.5Et2O are reported. Oxidation of each complex with ceric ion affords the corresponding FeIII ∼ CuII species. Variations in ligand design, the choice of co-ligand (chloride, bromide, trifluoromethanesulfonate (OTf) or solvent) and the choice of solvent allowed, in the case of acetonitrile solutions of [Cu(L1)(H2O)2](OTf)2, the close matching of the FeIII–FeII and CuII–CuI electrochemical couples. [Cu(L1)(H2O)2](OTf)2 reacts with dioxygen in acetonitrile, but is stable in other solvents such as tetrahydrofuran. Electronic spectra of the complex in acetonitrile exhibit a prominent ferrocenium ion band. These results are interpreted in terms of an intramolecular electron transfer equilibrium between FeII ∼ CuII and FeIII ∼ CuI tautomers for the complex that leads to it reacting with dioxygen; their possible biological relevance is discussed." @default.
- W2074153552 created "2016-06-24" @default.
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- W2074153552 date "2002-02-15" @default.
- W2074153552 modified "2023-10-16" @default.
- W2074153552 title "Copper complexes with ferrocenyl pendants: Evidence for an FeII ∼ CuII ⇌ FeIII ∼ CuI electron transfer equilibrium leading to a reaction with dioxygen" @default.
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- W2074153552 doi "https://doi.org/10.1039/b105150b" @default.
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