Mixed-valence Fe(III)Fe(IV) dimers. Preparation and physical properties of oxidation products of oxo-bridged binuclear iron(III) complexes

Воронкова, В. К.; Mroziński, Jerzy; Yampol'skaya, M. A.; Yablokov, Yu. V.; Evtushenko, N.S.; Byrke, M. S.; Gérbéléu, N. V.

doi:10.1016/0020-1693(95)04694-5

Cited by 20 publications

(2 citation statements)

References 26 publications

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“…In the reverse micelles, O 2 converts iron(III) TAML 1a into the heterovalent Fe III Fe IV dimer 3a via the simplified process of eq , assuming the μ-oxo bridged formulation. There are relatively few characterized Fe III Fe IV centers in synthetic complexes − ,− and metalloproteins, ,,, and this adds interest to the discovery of compound 3a . The reaction stoichiometry is rather unusual for iron–oxygen interactions , because one O 2 molecule formally requires eight iron(III) units for complete depositing its four electrons. Equation should be compared with the known process of eq in which iron(III) TAML activators are rapidly oxidized by O 2 in aprotic organic solvents to form the homovalent Fe IV Fe IV μ-oxo bridged dimer 2a .…”

Section: Resultsmentioning

confidence: 99%

Activation of Dioxygen by a TAML Activator in Reverse Micelles: Characterization of an Fe^IIIFe^IVDimer and Associated Catalytic Chemistry

et al. 2015

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Iron TAML activators of peroxides are functional catalase-peroxidase mimics. Switching from hydrogen peroxide (H2O2) to dioxygen (O2) as the primary oxidant was achieved by using a system of reverse micelles of Aerosol OT (AOT) in n-octane. Hydrophilic TAML activators are localized in the aqueous microreactors of reverse micelles where water is present in much lower abundance than in bulk water. n-Octane serves as a proximate reservoir supplying O2 to result in partial oxidation of FeIII to FeIV-containing species, mostly the FeIIIFeIV (major) and FeIVFeIV (minor) dimers which coexist with the FeIII TAML monomeric species. The speciation depends on the pH and the degree of hydration w0, viz., the amount of water in the reverse micelles. The previously unknown FeIIIFeIV dimer has been characterized by UV–vis, EPR, and Mössbauer spectroscopies. Reactive electron donors such as NADH, pinacyanol chloride, and hydroquinone undergo the TAML-catalyzed oxidation by O2. The oxidation of NADH, studied in most detail, is much faster at the lowest degree of hydration w0 (in “drier micelles”) and is accelerated by light through NADH photochemistry. Dyes that are more resistant to oxidation than pinacyanol chloride (Orange II, Safranine O) are not oxidized in the reverse micellar media. Despite the limitation of low reactivity, the new systems highlight an encouraging step in replacing TAML peroxidase-like chemistry with more attractive dioxygen-activation chemistry.

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Section: Resultsmentioning

confidence: 99%

Activation of Dioxygen by a TAML Activator in Reverse Micelles: Characterization of an Fe^IIIFe^IVDimer and Associated Catalytic Chemistry

et al. 2015

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“…For (4), this band occurs at 412 cm -1 shows medium intensity and is significantly broad which may be a result of Fe-O-Fe interaction [32,33].…”

Section: Infrared Spectramentioning

confidence: 97%

Solid complexes of iron(II) and iron(III) with rutin

2009

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Solid complex compounds of Fe(II) and Fe(III) ions with rutin were obtained. On the basis of the elementary analysis and thermogravimetric investigation, the following composition of the compounds was determined: (1)The coordination site in a rutin molecule was established on the basis of spectroscopic data (UV-Vis and IR). It was supposed that rutin was bound to the iron ions via 4C=O and 5C-oxygen in the case of (1) and (3). Groups 5C-OH and 4C=O as well as 3 0 C-OH and 4 0 C-OH of the ligand participate in binding metals ions in the case of (2). At an excess of iron(III) ions with regard to rutin under the synthesis conditions of (4), a side reaction of ligand oxidation occurs. In this compound, the ligands' role plays a quinone which arose after rutin oxidation and the substitution of Fe(II) and Fe(III) ions takes place in 4C=O, 5C-OH as well as 4 0 C-OH, 3 0 C-OH ligands groups. The magnetic measurements indicated that (1) and (3) are high-spin complexes.

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Increased Nuclearity of Salen‐Type Transition Metal Complexes by Incorporation of O‐Alkyloxime Functionality

Akine

Nabeshima

2014

Heteroatom Chemistry

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The effect of incorporation of O‐alkyloxime functionality in the salen‐type tetradentate ligand was investigated from a viewpoint of complexation behavior with cobalt(II), nickel(II), and zinc(II). The complexation of salamo ligands (H2salamo = 1,2‐bis(salicylideneaminooxy)ethane) with zinc(II) and cobalt(II) afforded trinuclear complexes [M3L2(OAc)2] (M = ZnII, CoII; L = salamo, 3‐MeOsalamo). The phenoxo groups of the two [ML] units coordinate to the third MII, which results in the trinuclear structure. Upon complexation with nickel(II) acetate, the parent H2salamo gave a trinuclear complex [Ni3(salamo)2(OAc)2(EtOH)2], whereas H2(3‐MeOsalamo) produced a mononuclear complex [Ni(3‐MeOsalamo)(H2O)2]. The salamo complexes described here are similar to the corresponding complexes with N,N′‐disalicylidene‐1,4‐diaminobutane (H2salbn), indicating that the difference between the –OCH2CH2O– and –(CH2)4– groups has a small influence on the structural features of the complexes. However, this difference affects the complexation process with zinc(II) acetate. The trinuclear complex [Zn3(3‐MeOsalamo)2(OAc)2] was formed cooperatively, whereas the imine analog [Zn3(3‐MeOsalbn)2(OAc)2] was not.

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Mixed-valence Fe(III)Fe(IV) dimers. Preparation and physical properties of oxidation products of oxo-bridged binuclear iron(III) complexes

Cited by 20 publications

References 26 publications

Activation of Dioxygen by a TAML Activator in Reverse Micelles: Characterization of an Fe^IIIFe^IVDimer and Associated Catalytic Chemistry

Activation of Dioxygen by a TAML Activator in Reverse Micelles: Characterization of an Fe^IIIFe^IVDimer and Associated Catalytic Chemistry

Solid complexes of iron(II) and iron(III) with rutin

Increased Nuclearity of Salen‐Type Transition Metal Complexes by Incorporation of O‐Alkyloxime Functionality

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Mixed-valence Fe(III)Fe(IV) dimers. Preparation and physical properties of oxidation products of oxo-bridged binuclear iron(III) complexes

Cited by 20 publications

References 26 publications

Activation of Dioxygen by a TAML Activator in Reverse Micelles: Characterization of an FeIIIFeIVDimer and Associated Catalytic Chemistry

Activation of Dioxygen by a TAML Activator in Reverse Micelles: Characterization of an FeIIIFeIVDimer and Associated Catalytic Chemistry

Solid complexes of iron(II) and iron(III) with rutin

Increased Nuclearity of Salen‐Type Transition Metal Complexes by Incorporation of O‐Alkyloxime Functionality

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Product

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Activation of Dioxygen by a TAML Activator in Reverse Micelles: Characterization of an Fe^IIIFe^IVDimer and Associated Catalytic Chemistry

Activation of Dioxygen by a TAML Activator in Reverse Micelles: Characterization of an Fe^IIIFe^IVDimer and Associated Catalytic Chemistry