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 15,165 document(s) hit in 31,850,051 MEDLINE articles (0.00 seconds)

Phenolate and phenoxyl radical complexes of a series of alkaline earth metal ions as well as monovalent cations such as Na+ and K+ have been prepared by using 2,4-di-tert-butyl-6-(1,4,7,10-tetraoxa-13-aza-cyclopentadec-13-ylmethyl)phenol (L1H) and 2,4-di-tert-butyl-6-(1,4,7,10,13-pentaoxa-16-aza-cyclooctadec-16-ylmethyl)phenol (L2H) to examine the effects of the cations on the structure, physicochemical properties and redox reactivity of the phenolate and phenoxyl radical complexes. Crystal structures of the Mg2+- and Ca2+-complexes of L1- as well as the Ca2+- and Sr2+-complexes of L2- were determined by X-ray crystallographic analysis, showing that the crown ether rings in the Ca2+-complexes are significantly distorted from planarity, whereas those in the Mg2+- and Sr2+-complexes are fairly flat. The spectral features (UV-vis) as well as the redox potentials of the phenolate complexes are also influenced by the metal ions, depending on the Lewis acidity of the metal ions. The phenoxyl radical complexes are successfully generated in situ by the oxidation of the phenolate complexes with (NH4)(2)[Ce4+(NO3)6] (CAN). They exhibited strong absorption bands around 400 nm together with a broad one around 600-900 nm, the latter of which is also affected by the metal ions. The phenoxyl radical-metal complexes are characterized by resonance Raman, ESI-MS, and ESR spectra, and the metal ion effects on those spectroscopic features are also discussed. Stability and reactivity of the phenoxyl radical-metal complexes are significantly different, depending on the type of metal ions. The disproportionation of the phenoxyl radicals is significantly retarded by the electronic repulsion between the metal cation and a generated organic cation (Ln+), leading to stabilization of the radicals. On the other hand, divalent cations decelerate the rate of hydrogen atom abstraction from 10-methyl-9,10-dihydroacridine (AcrH2) and its 9-substituted derivatives (AcrHR) by the phenoxyl radicals. On the basis of primary kinetic deuterium isotope effects and energetic consideration of the electron-transfer step from AcrH2 to the phenoxyl radical-metal complexes, we propose that the hydrogen atom abstraction by the phenoxyl radical-alkaline earth metal complexes proceeds via electron transfer followed by proton transfer.
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PMID:Effects of metal ions on physicochemical properties and redox reactivity of phenolates and phenoxyl radicals: mechanistic insight into hydrogen atom abstraction by phenoxyl radical-metal complexes. 1145 61

Redox-inactive metal ions play important roles in tuning chemical properties of metal-oxygen intermediates. Herein we report the effect of water molecules on the redox properties of a nonheme iron(III)-peroxo complex binding redox-inactive metal ions. The coordination of two water molecules to a Zn(2+) ion in (TMC)Fe(III) -(O2 )-Zn(CF3 SO3 )2 (1-Zn(2+) ) decreases the Lewis acidity of the Zn(2+) ion, resulting in the decrease of the one-electron oxidation and reduction potentials of 1-Zn(2+) . This further changes the reactivities of 1-Zn(2+) in oxidation and reduction reactions; no reaction occurred upon addition of an oxidant (e.g., cerium(IV) ammonium nitrate (CAN)) to 1-Zn(2+) , whereas 1-Zn(2+) coordinating two water molecules, (TMC)Fe(III) -(O2 )-Zn(CF3 SO3 )2 -(OH2 )2 [1-Zn(2+) -(OH2 )2 ], releases the O2 unit in the oxidation reaction. In the reduction reactions, 1-Zn(2+) was converted to its corresponding iron(IV)-oxo species upon addition of a reductant (e.g., a ferrocene derivative), whereas such a reaction occurred at a much slower rate in the case of 1-Zn(2+) -(OH2 )2 . The present results provide the first biomimetic example showing that water molecules at the active sites of metalloenzymes may participate in tuning the redox properties of metal-oxygen intermediates.
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PMID:Tuning the Redox Properties of a Nonheme Iron(III)-Peroxo Complex Binding Redox-Inactive Zinc Ions by Water Molecules. 2609 81

The rare-earth elements (Ln = Sc, Y, La-Lu) are widely used in stoichiometric and catalytic carbonyl group transformations. Sufficient availability, non-toxicity, high oxophilicity, tunable ion size/Lewis acidity and enhanced ligand exchangeability have been major driving factors for their successful implementation. Routinely employed reagents for stoichiometric carbonyl group transformations are divalent ytterbium and samarium compounds (e.g., ketone reduction), bimetallic CeCl3/LiR (C-C coupling), or ceric ammonium nitrate CAN (cyclic ketone oxidation). Rare-earth-metal triflates, and in particular Sc(OTf)3, are prominent examples of Lewis acid catalysts for versatile use in organic synthesis (e.g., Aldol and Michael reactions). Moreover, Ln(ii) and Ln(iii) complexes efficiently catalyze the (co)polymerization of carbonyl group-containing monomers including lactones, lactides, acrylates, and carbon dioxide. Featuring the most notorious greenhouse gas, CO2 is currently assessed as a cheap, abundant, and non-toxic C1 building block. Ln(iii) complexes are not only capable of efficient CO2 capture via reversible insertion but also of CO2 activation for catalytic conversions (copolymerization/cycloaddition with epoxides). This perspective focuses on structurally elucidated Ln complexes resulting from ketone or carbonyl derivative activation/insertion as well as carbon dioxide insertion products. The respective compounds will be sorted by structural motifs and, if applicable, details on reactivity and feasibility of catalytic reactions are presented. The article is subdivided in three parts: (i) donor and insertion products of ketones and aldehydes, (ii) redox-enhanced activation of carbonyl derivatives, and (iii) CO2 insertion/redox products and homogeneous catalytic conversion.
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PMID:Carbonyl group and carbon dioxide activation by rare-earth-metal complexes. 3323 14