Oxidation of the iron(II) complex with 3,5-dimethylpyrazole by air in acetonitrile and dibenzyl ether

Perova, E. V.; Нефедов, С. Е.; Chikhichin, D. G.; Kamalov, G. L.

doi:10.1134/s003602360912016x

Cited by 6 publications

(3 citation statements)

References 35 publications

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“…Recently [16], we have found that a reaction of the polymer complex [FeCl 2 (NCMe) 2 ] n with 3,5 dimeth ylpyrazole (HDmpz) yields a tetrahedral complex of the formula [Fe(HDmpz) 3 Cl]Cl, which is oxidized with air in acetonitrile into the binuclear complex The structures of the complexes under discussion were confirmed by X ray diffraction data.…”

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confidence: 55%

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Binuclear complexes with the “Chinese Lantern” geometry as intermediates in the liquid-phase oxidation of dibenzyl ether with atmospheric oxygen in the presence of copper(II) carboxylates

et al. 2012

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Reactions of copper(II) carboxylates with dibenzyl ether (DBE) gave binuclear complexes of the formula Cu 2 (µ OOCR) 4 (DBE) 2 (R = Bu t , Ph, and CF 3 ). The complexes were characterized by X ray dif fraction. The axial positions in the lantern type dimer are occupied by the coordinated DBE molecules. The complexes seem to be analogs of intermediate catalysts for the oxidation of DBE with atmospheric oxygen in the presence of transition metal complexes. When stored in air, the complex Cu 2 (µ OOCPh) 4 (DBE) 2 under went oxidation into Cu 2 (µ OOCPh) 4 (HOOCPh) 2 , which was characterized by X ray diffraction. The geom etry of its framework is similar; the structure is stabilized by intramolecular H bonds between the axially ori ented benzoic acid molecules and the adjacent bridging benzoate anions.

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“…Dibenzyl ether was purified by distilla tion in vacuo in an inert atmosphere as described in [16]. All manipulations involving the synthesis and isolation of the complexes were carried out under pure argon in dehydrated solvents, unless otherwise speci fied.…”

Section: Methodsmentioning

confidence: 99%

Binuclear complexes with the “Chinese Lantern” geometry as intermediates in the liquid-phase oxidation of dibenzyl ether with atmospheric oxygen in the presence of copper(II) carboxylates

et al. 2012

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“…Dibenzyl ether was purified as described in [5]. All manipulations involving the synthesis and iso lation of the complexes were carried out under pure argon in dehydrated solvents, unless otherwise speci fied.…”

Section: Methodsmentioning

confidence: 99%

Formation of the unusual cluster Cu4(μ4-OH)(μ-(CF3)2pz)4(μ-OOCPh)2(μ-OH)2(OH2)(Et3NH)[O(CH2Ph)2]2 in the thermolysis of a copper μ-aqua complex with bridging pyrazolate and acetate ligands in dibenzyl ether in the presence of atmospheric oxygen

Нефедов

Kushan

Yakovleva

et al. 2012

Russ. J. Inorg. Chem.

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A room temperature reaction of cupric acetate dihydrate with 3,5 bis(trifluoromethyl)pyrazole ((CF 3 ) 2 pzH) in chloroform in the presence of triethylamine gave a complex of the formula [Cu 2 (μ (CF 3 ) 2 pz) 2 (μ OH 2 )(OC(Me)OHNEt 3 )(OH 2 )(HCCl 3 )(OOCMe)(μ OOCMe)] 2 (2). Heating of this complex at 180°C in dibenzyl ether (DBE) in air yielded the tetranuclear pyrazolate benzoate cluster Cu 4 (μ 4 OH)(μ (CF 3 ) 2 pz) 4 (μ OOCPh) 2 (μ OH) 2 (OH 2 )(Et 3 NH)[O(CH 2 Ph) 2 ] 2 . It was suggested that such complexes can be intermediates in the liquid phase oxidation of DBE with atmospheric oxygen in the presence of copper com plexes containing pyrazolate bridges.

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Spontaneous Reduction of Mononuclear High‐Spin Iron(III) Complexes to Mononuclear Low‐Spin Iron(II) Complexes in Aqueous Media and Nuclease Activity via Self‐Activation

Ghosh

Tyagi

Dhara

2014

Chemistry An Asian Journal

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Mononuclear high-spin [Fe(III) (Pyimpy)Cl3 ]⋅2 CH2 Cl2 (1⋅2 CH2 Cl2 ) and [Fe(III) (Me-Pyimpy)Cl3 ] (2), as well as low-spin Fe(II) (Pyimpy)2 ](ClO4 )2 (3) and [Fe(II) (Me-Pyimpy)2 ](ClO4 )2 (4) complexes of tridentate ligands Pyimpy and Me-Pyimpy have been synthesized and characterized by analytical techniques, spectral, and X-ray structural analyses. We observed an important type of conversion and associated spontaneous reduction of mono-chelated high-spin Fe(III) (1⋅2 CH2 Cl2 and 2) complexes to low-spin bis-chelated Fe(II) complexes 3 and 4, respectively. This process has been explored in detail by UV/Vis, fluorescence, and (1) H NMR spectroscopic measurements. The high positive potentials observed in electrochemical studies suggested a better stabilization of Fe(II) centers in 3 and 4. Theoretical studies by density functional theory (DFT) calculations supported an increased stabilization for 3 in polar solvents. Self-activated nuclease activity of complexes 1⋅2CH2 Cl2 and 2 during their spontaneous reduction was examined for the first time and the mechanism of nuclease activity was investigated.

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Oxidation of the iron(II) complex with 3,5-dimethylpyrazole by air in acetonitrile and dibenzyl ether

Cited by 6 publications

References 35 publications

Binuclear complexes with the “Chinese Lantern” geometry as intermediates in the liquid-phase oxidation of dibenzyl ether with atmospheric oxygen in the presence of copper(II) carboxylates

Binuclear complexes with the “Chinese Lantern” geometry as intermediates in the liquid-phase oxidation of dibenzyl ether with atmospheric oxygen in the presence of copper(II) carboxylates

Formation of the unusual cluster Cu4(μ4-OH)(μ-(CF3)2pz)4(μ-OOCPh)2(μ-OH)2(OH2)(Et3NH)[O(CH2Ph)2]2 in the thermolysis of a copper μ-aqua complex with bridging pyrazolate and acetate ligands in dibenzyl ether in the presence of atmospheric oxygen

Spontaneous Reduction of Mononuclear High‐Spin Iron(III) Complexes to Mononuclear Low‐Spin Iron(II) Complexes in Aqueous Media and Nuclease Activity via Self‐Activation

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