Short-lived chemical species of57Fe in57Co-labelled Co/IO3/2 studied by time-resolved emission Mössbauer spectroscopy

Time resolved Mössbauer spectra were measured for⁵⁷Co-labelled Co/IO₃/₂ using a delayed coincidence technique. A life-time for unstable⁵⁷Fe(II)-species formed through EC-decay was estimated to be 43±5 ns at room temperature and the initial distribution of⁵⁷Fe(II)/⁵⁷Fe(III) at 14.4 keV nuclear level to be 0.47±0.13. The results are discussed in terms of electron transfer from the decayed⁵⁷Fe(II) atoms to iodate ions.     

Mössbauer Studies of Bispyridine Adducts of Fe(II), 57Fe-Doped Ni(II), Co(II) and 57Co-Labelled Co(II) β-Diketonates

The Mössbauer absorption and emission spectra of FeL₂Py₂, Fe-doped (⁵⁷Fe, M) (L)₂Py₂ and ⁵⁷CoL₂Py₂ (where, L=acac, dbm and hfa, M=Co or Ni) are reported. It was found that the Mössbauer parameters, especially, quadrupole splittings of ⁵⁷Fe in ⁵⁷CoL₂Py₂ exception of ⁵⁷Co(dbm)₂PY₂are quite similar to those of the corresponding (⁵⁷Fe, Co)L₂Py₂. In addition, the Mössbauer spectra shown that the chemical states of ⁵⁷Fe in the hosts of Fe(acac)₂Py₂, Co(acac)₂Py₂ and Ni(acac)₂Py₂ were not identical.     

Redox kinetics of metal complexes in nonaqueous solutions. V. Kinetics and mechanism of the iron (II) reduction of the acetylacetonates of manganese (III) and cobalt (III) in acetonitrile

The electron transfer step of the reduction of Mn(acac)₃ and Co(acac)₃ by Fe(II) in acetonitrile is preceded by the one-ended dissociation of an acac ligand and the formation of a binuclear bridged complex. After the electron transfer has taken place through the bridging ligand, the complex dissociates into the products M(acac)₂ (M = Mn, Co) and Fe(acac)²⁺. These primary reaction products could not be identified, since the transfer of acac from M(acac)₂ to Fe(acac)²⁺ is too rapid, producing ultimately Fe(acac)₃ and M²⁺. The M(III)-oxygen cleavage is accelerated by M(acac)₂. Furthermore, the dissociation of the binuclear intermediate is catalyzed by the M(acac)₃ reactant. Mn(acac)₃ is reduced more than a thousand times faster than Co(acac)₃.     

Mössbauer Studies of Bispyridine Adducts of Fe(II), 57Fe-Doped Ni(II), Co(II) and 57Co-Labelled Co(II) β-Diketonates

The Mössbauer absorption and emission spectra of FeL₂PY₂ Fe-doped (⁵⁷Fe₂M) (L)₂Py₂ and ⁵⁷CoL₂Py₂ (where, L=acac, dbm and hfa, M=Co or Ni) are reported. It was found that the Mössbauer parameters, especially, quadrupole splittings of ⁵⁷Fe in ⁵⁷CoL₂Py₂ exception of ⁵⁷Co(dbm)₂Py₂are quite similar to those of the corresponding (⁵⁷Fe, Co)L₂Py₂. In addition, the Mössbauer spectra shown that the chemical states of ⁵⁷Fe in the hosts of Fe(acac)₂PY₂, Co(acac)₂Py₂ and Ni(acac)₂Py₂ were not identical.     

Coincidence Mössbauer spectroscopic studies on57Co-labelled [CoFe2O(CH3CO2)6(H2O)3]

Coincidence Mössbauer spectra of⁵⁷Co-labelled [CoFe₂O(CH₃CO₂)₆(H₂O)₃] were determined at 78 K and 298 K with three timewindows of 0–50, 50–150 and 150–300 ns. Temperature dependence in the spectral shape ascribed to an intramolecular electron transfer was observed in all the time-window spectra, while little time dependence was observed. The results indicate that⁵⁷Fe atoms produced by EC-decay are incorporated in a chemical environment similar to that of the parent⁵⁷Co atoms, forming a trinuclear Fe^IIFe₂ ^III structure at an early stage after the EC-decay.after April 1, 1991.     

X-ray gated Mössbauer spectroscopic studies on57Co-labelled cobalt/II/ fluoride

KX-ray-gated emission Mössbauer spectra of⁵⁷Co-labelled CoF₂ and CoF₂.2H₂O were measured at room temperature, using the coincidence technique. A difference was found in the relative intensity of⁵⁷Fe(II)/⁵⁷Fe(III) between the X-ray-gated and non-gated emission spectra. The results are explained in terms of local radiolytic effects of water of crystallization and the chemical effects associated with the de-excitation processes caused by EC-decay.     

Effects of the host matrix on the 57Fe-species produced through EC-decay in 57Co-labelled tris(phenanthroline) cobalt (II) perchlorate.

Emission M?ssbauer spectroscopic studies of 57Co-labelled [Co(phen)3]clO4)2 in host matrices [M(II)(phen)3](ClO4)2(M=Co, Fe, and Ni) indicate that the relative intensities of the anomalous species produced through the EC-decay depend on the kind of the host matrix. The largest intensity was observed with the cobalt (II) matrix, and the smallest with the iron (II) matrix. Emission spectra of 57Co-labelled [Co(2-CH3-phen)3](ClO4)2 2H2O in the matrix of [Fe(2-CH3-phen)3](ClO4)2 were also studied. The high-spin state (5T2) was predominantly observed at 4.2 K in the emission spectrum, while the low-spin state (1A1) was mainly observed in the absorption spectrum at 78 K. The results are discussed in terms of the stability of the lattice.     

Radiation durability of aluminophosphate glass prepared for the stable storage of high-level nuclear wastes

⁵⁷Fe Mössbauer spectra of 30CaO·15Al₂O₃·5Fe₂O₃·25PbO·25P₂O₅ glass consist of two quadrupole doublets due to distorted Fe(III)O₆ and Fe(II)O₆ octahedra. Mössbauer spectra of the aluminophosphate glass irradiated with⁶⁰Co γ-rays (≈5·10⁴Gy) were essentially the same as those of non-irradiated glass. Mössbauer spectra of γ-ray irradiated aluminophosphate glass, containing 10 stable isotopes (Sr, Y, Zr, Nb, Mo, Ba, La, Ce, Pr, and Nd) as the simulated nuclear waste, were also the same as those of non-irradiated glass. These results indicate that the aluminophosphate glass containing iron and lead has high radiation-durability, in addition to high heat resistivity and high water resistivity.     

Temperature dependence of the mixed-valence state of57Fe-atoms produced in57Co-Labelled oxo-centered trinuclear iron acetate complexes

Emission Mössbauer spectra of mixedvalence trinuclear complexes,⁵⁷Co-labelled [CoFe₂O(CH₃CO₂)₆(H₂O)₃] and [CoFe₂O(CH₃CO₂)₆ (py)₃]py were compared with that of [CoCr₂O(CH₃CO₂)₆ (py)₃]py. It was found that the⁵⁷Fe atoms produced in⁵⁷Co-labelled [CoFe₂O(CH₃CO₂)₆(H₂O)₃] and [CoFe₂O(CH₃CO₂)₆ (py)₃]py showed a temperature-dependent mixed-valence state as observed in the absorption Mössbauer spectra of [Fe₃O(CH₃CO₂)₆ (H₂O)₃] and [Fe₃O(CH₃CO₂)₆ (py)₃]py, respectively, while⁵⁷Co-labelled [CoCr₂O(CH₃CO₂)₆ (py)₃]py showed a temperature-independent divalent iron/II/ state. The results indicate that the decayed atoms keep their position at the sites of original⁵⁷Co atoms and that the valence electrons are transferred through the intramolcular bondings.     

Mossbauer Spectroscopic Study of 57Co-Labelled Cobalt(II) Bisoxine Dihydrate

The chemical states of ⁵⁷Fe atoms in ⁵⁷Co-labelled cobalt(II) oxinate and in iron(II) oxinate have been studied by means of Mössbauer spectroscopy. Consquently the trivalent charge state of iron atom was found in ⁵⁷Co-labelled hydrated cobalt(II) oxinate, and remarkable difference in Mössbauer parameters of ferrous ion in ⁵¹Co-labelled cobalt(II) oxinate and iron(II) oxinate complexes are observed.     

Solvent and salt effects on the redox behaviour of trisacetylacetonato manganese(III)

The polarographic and voltammetric behaviour of trisacetylacetonato manganese(III) [Mn(acac)₃] has been studied in methanol, ethanol, tetrahydrofurane, butyrolactone, propylenecarbonate, N,N-dimethylformamide, acetonitrile, nitromethane, N-methylpyrrolidone(2), 1,2-dichloroethane, dichloromethane, dimethylsulfoxide and acetic acid, Mn(acac)₃ was found to undergo a reversible one-electron reduction to Mn(acac)₃^? in most of the solvents mentioned. A further reduction at very negative potentials has been also observed in several solvents. The oxidation of Mn(acac)₃ to Mn(acac)₃⁺ has been studied by cyclovoltammetry in dichloromethane, nitromethane, acetonitrile, propylenecarbonate, N-methylpyrrolidinone(2), N,N-dimethylformamide and dimethylsulfoxide. The polarographic behaviour of NaMn(acac)₃ and Mn(acac)₂ has been investigated in the seven solvents listed above as well as in methanol. The half-wave potentials and the peak potentials referred to bisbiphenylchromium(I)/bisbiphenylchromium(0) as a reference redox system were found to vary with the nature of the solvent. Conductivity studies of Mn(acac)₃ and NaMn(acac)₃ have been carried out in these solvents. U.v.-visible and near i.r. spectra have been recorded of Mn(acac)₃, NaMn(acac)₃, Mn(acac)₂ and Na(acac) in the solvents mentioned. It has further been observed that the half-wave potentials for the polarographic reduction of Mn(acac)₃ shifted to more positive values by the addition of alkali metal ions and to more negative values by the addition of halide ions. The interactions of the solvent with Mn(acac)₃ and the variation of redox potentials with both the solvent and the added electrolytes will be discussed.     

Kinetics and mechanism of acetylacetonate transfer from acetylacetonatomanganese(III) to iron(III) in acetonitrile catalysis and inhibition effects

The reaction between tris(acetylacetonato)magnanese(III) and hexa(N,N-dimethylformamide)iron(III) perchlorate in acetonitrile proceeds in two stages. The first stage corresponds to the reaction of pentacoordinated Fe(DMF) with Mn(acac)₃, and the rate-determining step of the second stage consists mainly in the elimination of a DMF ligand from Fe(DMF) to yield Fe(DMF) which reacts rapidly with the manganese complex. The formation of Fe(DMF) is catalyzed by Mn(acac)₃, this catalytic effect being decreased by manganese products. The rate-determining step for the formation of Fe(acac)₃ is the transfer of the first acetylacetonate to yield Fe(acac)²⁺. The final products of iron depend on the ratio of reactant concentrations. With Mn or Fe in excess, Fe(acac)₃ or Fe(acac)²⁺ are mainly produced.     

Study of the incorporation of carrier-free57Co in Fe(II) and Mn(II) oxalates by a double radioactive tracer method

The incorporation of carrier-free⁵⁷Co²⁺ by coprecipitation in Fe and Mn oxalato compounds is characterized by a double radioactive tracer method. This is achieved by labelling the host compound with a short-lived tracer,⁵²Fe or⁵²Mn. Activity ratios are measured at several stages, during the precipitation and, afterwards, during the dissolution of the solid. In any case, results indicate very large incorporation yields of⁵⁷Co in the precipitate, independently from the intrinsic precipitation yield of the host compound. The observation of a continuous distribution of dopant atoms in the matrix in coprecipitation and dissolution experiments allows to rule out the adsorption of the doping species on a pre-existing precipitate of the host compound and accounts for isomorphous replacement. Incorporation of⁵⁷Co in Fe(II) oxalate follows a logarithmic distribution law, giving rise to a concentration gradient of dopant species in the precipitate. Dopant atoms are found to be concentrated in the internal layers of the crystals.     

Hyperfine structure measurements of the metastable (3d 6 4s 2)3 H 4, 5, 6 states of57Fe: Configuration interaction in the hyperfine structure of the iron atom

We report the hyperfine structure (hfs) measurement of the metastable (3d ⁶ 4s ²)a ³ H _{4, 5, 6} states of⁵⁷Fe. The kHz-precision of these experimental results together with the hyperfine structure values of (3d ⁶ 4s ²)a ⁵ D _{1, 2, 3, 4}, (3d ⁷ 4s)a ⁵ F _{2, 3, 4, 5}, and (3d ⁷ 4s)a ³ F _{2, 3, 4}, which were measured earlier, allowed to determine a very detailed set of effective radial parameters describing the hfs of these states, using a new parametrization method. This method treats one- and two-body contributions to the hfs separately. In this way configuration interaction effects in the hfs of the⁵⁷Fe atom can be studied in detail and compared with configuration interaction effects in the fine structure of the same atom.     

Oxidative thermolysis of Mn(acac)3 on the surface of γ-alumina support

Precipitated γ-alumina support was decorated with Mn(acac)₃ by incipient wetness impregnation with toluene solutions containing Mn(acac)₃ in amount equivalent to loading of 0.35, 0.74, 1.38, 2.38 and 3.50 Mn(acac)₃ moleculs per nm² of the support. In order to evaluate the mechanism of Mn(acac)₃ interaction with the surface of γ-alumina support and subsequent transformations of the supported Mn(acac)₃ species, oxidative thermolysis of Mn(acac)₃/Al₂O₃ samples in air was studied by diffuse reflectance FTIR, thermogravimetric analysis (TG/DTG), differential thermal analysis (DTA) and XRD. It has been found out that decoration of γ-Al₂O₃ support with Mn(acac)₃ results in the formation of surface bound Mn(acac)_3−x species when Mn(acac)₃ loading does not exceed 1.38 Mn(acac)₃/nm². At higher Mn(acac)₃ loading the formation of the supported bulk-like Mn(acac)₃ species also occurs. The interaction of Mn(acac)₃ molecules with the support surface occurs via substitution of acetylacetonate ligand(s) with the oxygen atom of surface hydroxyl group(s) accompanied by elimination of acetylacetone molecules. The evolved acetylacetone reacts with the alumina surface that results in the formation of surface Al(acac)_3−x species. The oxidative thermolysis of Mn(acac)_3−x species on the surface of γ-alumina proceeds via partial elimination of acetylacetonate ligands and partial oxidation of the remaining ligands without destruction of their cyclic structure within 425-550 K. The complete oxidative destruction of acetylacetonate ligands takes place within 600-700 K and results in the formation of manganese oxide species on the alumina surface. The dispersed surface manganese oxide species originate upon the oxidative thermolysis of the surface bound Mn(acac)_3−x species while crystalline Mn₂O₃ phase results from the supported bulk-like Mn(acac)₃ species.     

Catalytic Action of Metallic Salts in Autoxidation and Polymerization. VII. Polymerization of Methyl Methacrylate by Cobalt(ll) or (III) Acetylacetonate-Dioxane Hydroperoxide

Abstract

Polymerization of methyl methacrylate by Co(II or III) acetylacetonate-dioxane hydroperoxide [abbreviated as Co(acac)2, Co(acac)₃, and DOX HPO, respectively] was carried out in dioxane solvent, and the differences in polymerization rate and the degree of polymerization between two initiating systems were compared. Co(acac)₂-DOX HPO for the initiation of the polymerization system was more effective than Co(acac)₃-DOX HPO. The polymerization rate equations for both initiating systems obtained from kinetic data were as follows. For Co(acac)₂-DOX HPO initiating system: R_p=k [M]^3/2[Co(acac)₂]^1/7[DOX HPO]^?     

Anomalous spin state of iron(II) in 57Fe Mössbauer emission spectra of 57Co-Labeled tris(2-methylphenanthroline) cobalt(II) perchlorate

⁵⁷Fe Mössbauer emission spectra of the ⁵⁷Co labeled complex compound [⁵⁷Co(2-CH₃-phen)₃] (ClO₄)₂·2H₂O have been measured as a function of temperature between 293 and 4.6 K. The spectra exclusively show high-spin iron(II) resonances beside a small fraction of an high-spin iron(II) species, whereas the corresponding iron(II) compound is known to exhibit thermally induced high-spin ⁵T_2g(O_h) ? low spin ¹A_1g(O_h) transition. The electronic nature of the anomalous spin state has been found to be ⁵A₁(D₃) by a theoretical treatment of the temperature dependence of the quadrupole splitting. The results are in good agreement with those obtained from Mössbauer absorption measurements on [⁵⁷Fe_0.01Co_0.99(2-CH₃-(phen)₃] (ClO₄)₂·2H₂O.     

Mössbauer study of paramagnetic relaxation effect in mixed crystals: High spin Fe3+ compounds diluted in diamagnetic hosts

The⁵⁷Fe Mössbauer spectra were measured in mixed crystals with different types of chemical bonding and crystal structure, i.e., (Fe,Al)(acac)₃, (Fe,Co)(acac)₃, K₃[(Fe,Al)(ox)₃]3H₂O, and NH₄(Fe,Al)(SO₄)₂12H₂O. The broadening of Mössbauer linewidth with increasing Fe³⁺–Fe³⁺ distance became less enhanced in the order: (Fe,Al)(acac)₃>(Fe,Co)(acac)₃, or K₃[(Fe,Al)(ox)₃]3H₂O>(Fe,Al)(acac)₃>NH₄(Fe,Al)(SO₄)₂12H₂O. Furthermore, it was found that the broadening of the linewidth was larger in neat tris (-diketonato) iron(III) complexes than in (Fe,Al)(acac)₃. Based on these results, the determining factors of the paramagnetic relaxation time other than Fe³⁺–Fe³⁺ distance and temperature were examined in terms of the Mössbauer linewidth as an indicator.     

Hexamminmetall(III)-hexachlorochromate(III): Darstellung,Kristallgitter und Spektren

Hexammine-metal(III) hexachlorochromates(III). Preparation, crystal lattic and spectra The preparation of [Me(NH₃)₆]CrCl₆ with Me = Co and Rh from aqueous solutions and with Me = Co, Cr and Rh by thermal dehydratation is given. The crystal structure of these compounds is T_h⁶? Pa3, Z = 4. The absorption spectrum shows the two known spin allowed bands at 13300 and 1890C cm^?1. Some weak vibronic absorptions are observed from 13870 cm^?1 to 15130 cm^?1. The vibrational spectrum of CrCl₆^2? has been completed by the measurement of the RAMAN spectrum, the IR spectra have been reinvestigated. The vibrational spectra confirm the nearly undisturbed octahedral symmetry of the hexahalogenometallate anion which has previously been observed for similar compounds.     

The mass spectra of 1,1,1-trichloro-2,4-pentanedione and its Al(III), Cr(III), Fe(III), Mn(II), Co(II) and Cu(II) complexes

The compounds 1,1,1-trichloro-2,4-pentanedione, Cu(II)tca₂, Co(II)tca₂, Mn(II)tca₂, Al(III)tca₃, Cr(III)tca₃ and Fe(III)tca₃ (tca?1,1,1-trichloro-2,4-pentanedionato, [CCl₃COCHCOCH₃]^?) have been prepared and their mass spectra have been obtained. The mass spectral results have been compared with findings for comparable fluorinated and nonhalogenated compounds. Comparisons are made in terms of internal redox reactions and hard and soft acid base theory. Rearrangement of chloride from ligand to metal accompanied by the elimination of CO or other neutral even electron fragments emerges as an important reaction for the ions of these compounds. While the internal redox reactions characteristic of all previous β-diketonate complex mass spectra still occur, their importance appears reduced to some degree by the facility of the chlorine rearrangement.