Thermal and spectral studies of 2,4,5-trimethoxybenzoates of heavy lanthanides(III) and yttrium(III)

2,4,5-Trimethoxybenzoates of Tb(III), Dy(III), Ho(III), Er(III), Tm(III), Yb(III), Lu(III) and Y(III) are crystalline, hydrated salts with colours typical for M(III) ions. The carboxylate group is a bidenate, chelating ligand. The complexes of Tb(III), Dy(III) and Ho(III) are dihydrates while those of Er(III), Tm(III), Yb(III), Lu(III) and Y(III) are trihydrates. These compounds are characterized by low symmetry. On heating in air to 1273 K, the 2,4,5-trimethoxybenzoates of heavy lanthanides(III) and yttrium(III) decompose in two steps. At first they dehydrate to form anhydrous salts which next are decomposed to the oxides of the respective metals. The values of the enthalpy of dehydration process were determined. The solubility in water at 293 K for all heavy lanthanides(III) and yttrium(III) are in the orders of 10^-3-10^-4 mol dm^-3. The magnetic moments of the complexes were determined in the temperature range 77-300 K.     

Synthesis and electrochemical properties of bipyrimidine bridged triruthenium complexes

A new μ(4)-bpym-bridged dimer of an oxoacetao-triruthenium complex with carbonyl, [{Ru(3)O(CH(3)COO)(5)(CO)(py)}(2)(μ(4)-bpym)], was synthesized. The complex possesses two stable mixed-valence states associated with Ru(3)(III,III,II)/Ru(3)(III,II,II) and Ru(3)(III,III,III)/Ru(3)(III,III,II). The IR-spectroelectrochemistry reveals ν(CO) spectra in five oxidation states, Ru(3)(III,III,III)-Ru(3)(III,III,III) to Ru(3)(III,II,II)-Ru(3)(III,II,II) and both the mixed-valence states show a spectrum indicating medium interaction between the Ru(3) units.     

Syntheses, Structures, and Spectroscopic Properties of Plutonium and Americium Phosphites and the Redetermination of the Ionic Radii of Pu(III) and Am(III)

A series of isotypic rare earth phosphites (RE = Ce(III), Pr(III), Nd(III), Pu(III), or Am(III)) with the general formulas RE(2)(HPO(3))(3)(H(2)O) along with a Pu(IV) phosphite, Pu[(HPO(3))(2)(H(2)O)(2)], have been prepared hydrothermally via reactions of RECl(3) with phosphorous acid. The structure of RE(2)(HPO(3))(3)(H(2)O) features a face-sharing interaction of eight- and nine-coordinate rare earth polyhedra. By use of the crystallographic data from the isotypic series along with data from previously reported isotypic series, the ionic radii for higher coordinate Pu(III) and Am(III) were calculated. The (VIII)Pu(III) radius was calculated as 1.112 ± 0.004 ?, and the (IX)Pu(III) radius was calculated to be 1.165 ± 0.002 ?. The (VIII)Am(III) radius was calculated as 1.108 ± 0.004 ?, and the (IX)Am(III) radius was calculated as 1.162 ± 0.002 ?.     

Columinescence effect in macromolecular complexes of Eu(III) and Tb(III)

The effect of Y(III) and Gd(III) coactivator ions on the intensity of Eu(III) and Tb(III) luminescence in monomer and polymer mixed-metal complexes was studied. Isomorphic replacement of Eu(III) and Tb(III) ions by Y(III) and Gd(III) ions in macromolecular complexes led to sensitization of Eu(III) and Tb(III) ion luminescence. A mechanism of columinescence was suggested. It involves a charge transfer and the ligand orbitals and the vacant orbitals of Eu(III) and Tb(III) ions and coactivators.     

Simultaneous determination of aluminoxamine and ferrioxamine in post-hemodialysis fluids by spectrophotometry and multivariate calibration

A spectrophotometric method for simultaneous determination of Al(III) and Fe(III) using the chelator Desferal® (desferrioxamine B) was developed. Partial least squares (PLS) regression was performed to resolve the overlapped signals obtained from Al(III) and Fe(III) complexes. The parameters controlling behavior of the system were investigated and optimum conditions were selected. PLS was the choice for the analysis of binary mixtures of Fe(III) and Al(III) over the range of 0.1 to 0.8 mg L^?1 by using the data of first derivative spectra. Absorbance data were taken between 200 and 600 nm. The calculated sensitivity values for the multivariate method were 4.88 and 5.64 for Al(III) and Fe(III), respectively. Multivariate detection limits were 0.075 and 0.064 mg L^?1 for Al(III) and Fe(III), respectively. The method was applied to real post-hemodialysis samples, and sample digestion by UV irradiation was discussed.     

meso Substituent effects on the geometric and electronic structures of high-spin and low-spin iron(III) complexes of mono-meso-substituted octaethylporphyrins

Introduction of a single meso substituent into ClFe(III)(OEP) or K[(NC)(2)Fe(OEP)] results in significant changes in the geometric and/or spectroscopic properties of these complexes. The mono-meso-substituted iron(III) complexes ClFe(III)(meso-Ph-OEP), ClFe(III)(meso-n-Bu-OEP), ClFe(III)(meso-MeO-OEP), ClFe(III)(meso-Cl-OEP), ClFe(III)(meso-NC-OEP), ClFe(III)(meso-HC(O)-OEP), and ClFe(III)(meso-O(2)N-OEP) have been isolated and characterized by their UV/vis and paramagnetically shifted (1)H NMR spectra. The structures of both ClFe(III)(meso-Ph-OEP) and ClFe(III)(meso-NC-OEP) have been determined by X-ray crystallography. Both molecules have five-coordinate structures typical for high-spin (S = 5/2) iron(III) complexes. However, the porphyrins themselves no longer have the domed shape seen in ClFe(III)(OEP), and the N(4) coordination environment possesses a slight rectangular distortion. These high-spin, mono-meso-substituted iron(III) complexes display (1)H NMR spectra in chloroform-d solution which indicate that the conformational changes seen in the solid-state structures are altered by normal molecular motion to produce spectra consistent with C(s) molecular symmetry. In pyridine solution the high-spin six-coordinate complexes [(py)ClFe(III)(meso-R-OEP)] form. In methanol solution in the presence of excess potassium cyanide, the low-spin six-coordinate complexes K[(NC)(2)Fe(III)(meso-R-OEP)] form. The (1)H NMR spectra of these show that electron-donating substituents produce an upfield relocation of the meso-proton chemical shifts. This relocation is interpreted in terms of increased contribution from the less common (d(xz),d(yz))(4)(d(xy))(1) ground electronic state as the meso substituent becomes more electron donating.     

Structure,insertion electrochemistry,and magnetic properties of a new type of substitutional solid solutions of copper,nickel, and iron hexacyanoferrates/hexacyanocobaltates

Substitutional solid solutions of metal hexacyanometalates in which low-spin iron(III) and cobalt(III) ions populate the carbon-coordinated sites were synthesized and studied by powder diffraction including Rietveld refinement, cyclic voltammetry of immobilized microparticles, diffuse reflection vis-spectrometry, and magnetization techniques. The continuous solid solution series of potassium copper(II), potassium nickel(II), and iron(III) [(hexacyanoferrate(III))(1-x)(hexacyanocobaltate(III))(x)] show that the substitution of low-spin iron(III) by cobalt(III) in the hexacyanometalate units more strongly affects the formal potentials of the nitrogen-coordinated copper(II) and high-spin iron(III) ions than those of the remaining low-spin iron(III) ions. In the case of copper(II) and iron(III) [(hexacyanoferrate(III))(1-x)(hexacyanocobaltate(III))(x)] the peak currents decrease much more than can be explained by stoichiometry, indicating that the charge propagation is slowed by the substitution of low-spin iron(III) by cobalt(III). The Rietveld refinement of all compounds confirmed the structure initially proposed by Keggin for Prussian blue and contradicts the structure described later by Ludi. The dependencies of lattice parameters on composition exhibit in all series of solid solutions studied similar, although small, deviations from ideality, which correlate with the electrochemical behavior. Finally, a series of solid solutions of the composition KNi(0.5)(II)Cu(0.5)(II)[Fe(III)(CN)(6)](1-x)[Co(III)(CN)(6)](x), where both the nitrogen- and carbon-coordinated metal ions are mixed populated and were synthesized and characterized. These are the first examples of solid solutions of metal hexacyanometalates with four different metal ions, where both the nitrogen- and the carbon-coordinated sites possess a mixed population.     

Complexation studies of iodides of trivalent uranium and lanthanides (Ce and Nd) with 2,2'-bipyridine in anhydrous pyridine solutions

In anhydrous pyridine solution at 294 K, U(III) and Ce(III) triiodides were found to form both 1:1 (ML) and 1:2 (ML(2)) complexes with bipyridine (bipy = L) while Nd(III) triodide formed only a 1:2 complex. The 1:3 (ML(3)) complexes were identified at low temperature with a large excess of L. Conductometry measurements showed for U(III) a large increase in the conductivity when increasing the molar ratio L:U. The complex UL(2) was found to be a 1:1 electrolyte and the species UI(2)(+) was more reactive toward L in comparison with UI(3). For Ce(III) and Nd(III), MI(2)(+) and MI(3) present about the same affinity for L. The stability of the complexes is limited, and U(III) possesses a slightly higher affinity for bipy than the trivalent lanthanides. Interestingly, a preference for the formation of ML(2) complex was shown for all the studied M(III) ions. The driving force for complex formation was always the enthalpy, and, surprisingly for a bidendate ligand (bipy), no favorable entropy contribution to complex formation was observed. The X-ray crystal structures of [CeI(3)(bipy)(2)(py)](4).5py.bipy and UI(3)(bipy)(2)(py).2py were determined. The structures of the molecules MI(3)(bipy)(2)(py) are almost identical for U and Ce. The mean M(III)-N(bipy) bond distances are equal to 2.67(3) A for Ce(III) and 2.65(4) A for U(III). The slightly smaller M(III)-N(bipy) distances observed for U(III) would reflect a slightly more important covalent character of the U(III)-N(bipy) bonds, in agreement with the slightly better affinity of U(III) than Ce(III) or Nd(III) toward bipy observed in solution and with the fact that the enthalpy is the driving force for complex formation.     

Synthesis and properties of oxo-carboxylato- and dioxo-bridged diosmium complexes of tris(2-pyridylmethyl)amine

A series of oxo-bridged diosmium complexes with tpa ligand (tpa = tris(2-pyridylmethyl)amine) are synthesized. The hydrolytic reaction of the mononuclear osmium complex [Os(III)Cl(2)(tpa)]PF(6) in aqueous solution containing a sodium carboxylate yields a μ-oxo-μ-carboxylato-diosmium(III) complex, [Os(III)(2)(μ-O)(μ-RCOO)(tpa)(2)](PF(6))(3) (R = C(3)H(7) (1), CH(3) (2), or C(6)H(5) (3)). One-electron oxidation of 1 with (NH(4))(2)Ce(IV)(NO(3))(6) gives a mixed-valent [Os(III)Os(IV)(μ-O)(μ-C(3)H(7)COO)(tpa)(2)](PF(6))(4) complex (4). A mixed-valent di-μ-oxo-diosmium complex, [Os(III)Os(IV)(μ-O)(2)(tpa)(2)](PF(6))(3) (5), is also synthesized from 1 in an aerobic alkaline solution (pH 13.5). All the complexes exhibit strong absorption bands in a visible-near-infrared region based on interactions of the osmium dπ and oxygen pπ orbitals of the Os-O-Os moiety. The X-ray crystallographic analysis of 1, 3, and 4 shows that the osmium centers take a pseudo-octahedral geometry in the μ-oxo-μ-carboxylato-diosmium core. The mixed-valent osmium(III)osmium(IV) complex 4 has a shorter osmium-oxo bond and a larger osmium-oxo-osmium angle as compared with those of the diosmium(III) complex 1 having the same bridging carboxylate. Crystal structure of 5 reveals that the two osmium ions are bridged by two oxo groups to give an Os(2)(μ-O)(2) core with the significantly short osmium-osmium distance (2.51784(7) ?), which is indicative of a direct osmium-osmium bond formation with the bond order of 1.5 (σ(2)π(2)δ(2)δ*(2)π*(1) configuration). In the electrochemical studies, the μ-oxo-μ-carboxylato-diosmium(III) complexes exhibit two reversible Os(III)Os(III)/Os(III)Os(IV) and Os(III)Os(IV)/Os(IV)Os(IV) oxidation couples and one irreversible redox wave for the Os(III)Os(III)/Os(II)Os(III) couple in CH(3)CN. The irreversible reductive process becomes reversible in CH(3)CN/H(2)O (1:1 Britton-Robinson buffer; pH 5-11), where the {1H(+)/2e(-)} transfer process is indicated by the plot of the redox potentials against the pH values of the solution of 1. Thus, the μ-oxo-μ-butyrato-diosmium(III) center undergoes proton-coupled electron transfer to yield a μ-hydroxo-μ-butyrato-diosmisum(II) species. The di(μ-oxo) complex 5 exhibits one reversible Os(III)Os(IV)/Os(IV)Os(IV) oxidation process and one reversible Os(III)Os(IV)/Os(III)Os(III) reduction process in CH(3)CN. The comproportionation constants K(com) of the Os(III)Os(IV) states for the present diosmium complexes are on the order of 10(19). The values are significantly larger when compared with those of similar oxo-bridged dimetal complexes of ruthenium and rhenium.     

Synthesis of rare-earth metal-containing polymers and their fluorescence properties

Four kinds of polymeric β-diketone compounds, including poly(vinylbenzyldibenzoylmethane)(1), poly(vinylbenzylacetoacetone)(2), poly(vinylbenzyl-2-thenoyltrifluoroacetone)(3) and poly(p-benzoylacetylstyrene)(4) were synthesized. And then polymeric β-diketone-europium(III), -terbium(III), -samarium(III), -dysprosium(III), -europium(III)-gadolinium(III), -terbium(III)-gadolinium(III), and -europium(III)-terbium(III) chelates were also synthesized. The chelate structures were confirmed. The influence of the structure on the fluorescence properties was investigated. The fluorescence intensity of polymeric rare-earth metal complexes is closely related to the ligand and metal content. Polymeric complexes possess a higher fluorescence stability than that of corresponding low-molecular-weight complexes.     

Extraction and separation of bismuth(III) from steel and bismuth-base alloys

Summary Separation of bismuth(III) from iron(III), molybdenum(VI), vanadium(V), chromium(VI), titanium(IV), antimony(III), lead(II), beryllium(II), uranium(VI), hafnium(IV), indium(III) and zirconium (IV) is achieved by solvent extraction with high molecular weight amines from sodium succinate solution adjusted to suitable pH. Bismuth(III) is stripped from the organic phase and determined spectrophotometrically. The method is shown to be applicable to bismuth alloys.

---

Extraktion und Trennung von Wismut(III) aus Stahl und wismuthältigen Legierungen

Zusammenfassung Wismut(III) läßt sich von Fe(III), Mo(VI), V(V), Cr(VI), Ti(IV), Sb(III), Pb(II), Be(II), U(VI), Hf(IV), In(III) und Zr(IV) durch Extraktion mit hochmolekularen Aminen aus Natriumsuccinat bei geeignetem pH trennen. Bi(III) wird dann von der organischen Phase getrennt und spektralphotometrisch bestimmt. Das Verfahren eignet sich für Wismutlegierungen.

     

Hydrated structures and dehydration processes of lanthanoid(III) chloranilates studied by EXAFS

The local structures of lanthanoid(III) chloranilate complexes of Pr(III), Nd(III), Tb(III) and Er(III) have been studied by EXAFS (extended X-ray absorption fine structure). Hydrated structures of the lanthanoid(III) ions in these complexes have been investigated with respect to their coordination numbers and interatomic distances. Six or four water molecules coordinate to the lanthanoid(III) ion of Pr(III) or Nd(III), respectively, just after preparation of the complexes. The temperature dependence of the first coordinated structures has been studied in order to reveal the behavior of the coordinated water molecules in dehydration process. The coordination number around the central lanthanoid(III) ion decreases stepwise as temperature increases, depending on the type of central lanthanoid(III) ion present. The interatomic distance between the central lanthanoid(III) ion and oxygen atoms in the first shell decreases, accompanying the decrease of the coordination numbers. A parameter representing proportion shows the reduction of interatomic distance as one coordinated water molecule removes from the central ion, depending on the type of lanthanoid(III) ions.     

Mixed chelates of some trivalent lanthanide ions containing (trans-1,2-cyclhexylenedinitrilo)tetraacetate and norleucinate

Summary Formation constants of mixed chelates with (trans-1,2-cyclohexylenedinitrilo)tetra-acetate (DCTA) as primary ligand and norleucinate (nle) as secondary ligand with metal ions La(III), Ce(III), Pr(III), Sm(III), Gd(III), Tb(III), Dy(III), Er(III), and Yb(III) have been determined by the modified potentiometricpH titration method of Irving-Rossotti in aqueous medium at (295±1) K and fixed ionic strength of =0.1M (NaClO₄). Formation constants of binary complexes of the metal ions with the secondary ligand have also been determined under identical conditions. The mixed chelates were found to be more stable than the binary ones. The order of stabilities in terms of metal ions is La(III)Gd(III)

Gemischte Chelate einiger dreiwertiger Lanthanidenionen mit (trans-1,2-Cyclohexylendinitril)tetraacetat und Norleucinat

Zusammenfassung Es wurden die Komplexbildungskonstanten gemischter Chelate mit (trans-1,2-Cyclohexylendinitril)tetraacetat als Primärkomponente und Norleucinat als Sekundärkomponente mit den Metallionen La(III), Ce(III), Pr(III), Sm(III), Gd(III), Tb(III), Dy(III), Er(III) und Yb(III) mittels einer modifizierten potentiometrischen Titrationsmethode nach Irving-Rossotti in wäßrigem Medium bei (295±1) K und einer konstanten Ionenstärke von =0.1M (NaClO₄) bestimmt. Die Bildungskonstanten der binären Komplexe der Metallionen mit dem Sekundärliganden wurden ebenfalls unter identen Bedingungen bestimmt. Es wurde festgestellt, daß die gemischten Chelate stabiler sind als die binären. Die Stabilitätsreihenfolge bezüglich der Metallionen ist La(III)Gd(III)     

Separation and preconcentration of gallium(III), indium(III), and thallium(III) using new hydrazone-modified resin.

Ga(III), In(III) and Tl(III) ions in the presence of different sulfate salts have been successfully separated using 1-(3,4-dihydroxybenzaldehyde)-2-acetylpyridiniumchloride hydrazone (DAPCH) loaded on Duolite C20 in batch and column modes. The obtained modified resin as well as the metal complexes was characterized by elemental analysis and infrared spectra. The extraction isotherms were determined at different pH values. Ga(III) and In(III) are sorbed from aqueous solution at pH 2.5 - 3.0 while Tl(III) is sorbed at 2.0. The stripping of the adsorbed ions can be carried out using different concentrations of HCl as eluent. The saturation sorption capacities of Ga(III), In(III) and Tl(III) were 0.82, 0.96 and 0.44 mmol g(-1), where the preconcentration factors are 150, 150 and 100, respectively. The metal(III):Duolite C20-DAPCH ratio was 1:2 for Tl(III) and 1:1 for In(III) and Ga(III). The loaded resin can be regenerated for at least 50 cycles. The utility of the modified resin was tested in aqueous samples and the results show an RSD value of < 5% reflecting their accuracy and reproducibility.     

Adsorption behaviour of scandium,yttrium, cerium and uranium from xylenol orange solutions onto anionexchange resins

The effects of concentration, pH and anions on the adsorption behaviour of xylenol orange (XO) on the strong anion exchangers, Amberlite IRA-400 and Hitachi 2632 are described. The adsorption behaviour of the XO complexes of Ce(III), Y(III), Sc(III) and U(VI) on the Amberlite IRA-400 resin as a function of XO concentration and pH is reported. A continuous-flow radiometric detector is used to investigate the separations of the Ce(III)—Sc(III), Y(III)—Sc(III), and Ce(III)—Y(III) pairs on the XO-form Hitachi 2632 resin column by pH control. Satisfactory separations of the Ce(III)—Sc(III) and Y(III)—Sc(III) pairs are achieved.     

Reactions and phases within the TeO2-rich part of the Bi2O3-TeO2 system

The complexes of heavy lanthanides and yttrium with 2,3-dimethoxybenzoic acid of the formula: Ln(C₉h₉O₄)₃·nH₂O, where Ln=Tb(III), Dy(III), Ho(III), Er(III), Tm(III), Yb(III), Lu(III), Y(III), and n=2 for Tb(III), Dy(III), Ho(III), Y(III), n=1 for Er(III), Tm(III), n=0 for Yb(III) and Lu(III) have been synthesized and characterized by elemental analysis, ir spectroscopy, thermogravimetric studies and x-ray diffraction measurements. The complexes have colours typical for Lnł³⁺ ions (Tb(III), Dy(III), Tm(III), Yb(III), Lu(III), Y(III) - white; Ho(III) - cream and Er(III) - salmon). the carboxylate groups in these complexes are a symmetrical, bidentate, chelating ligand or tridentate chelating-bridging. they are isostructural crystalline compounds characterized by low symmetry. On heating in air to 1273 k the 2,3-dimethoxybenzoates of heavy lanthanides and yttrium decompose in various ways. The complexes of Tb(III), Dy(III), Ho(III), Er(III), Tm(III) and Y(III) at first dehydrate to form anhydrous salts which next are decomposed to the oxides of the respective metals. 2,3-dimethoxybenzoates of Yb(III) and Lu(III) are directly decomposed to oxides. When heated in nitrogen the hydrates also dehydrate in one step to form the anhydrous complexes that next form the mixture of carbon and oxides of respective metals or their carbonates. The solubility of the yttrium and heavy lanthanide 2,3-dimethoxybenzoates in water at 293 k is of the order of 10^-2 mol dm^-3. This revised version was published online in July 2006 with corrections to the Cover Date.     

Ion-chromatographic analysis of mixtures of ferrous and ferric iron

Determinations of the aqueous iron species Fe(II) and Fe(III) are essential for a fully-informed understanding of redox processes involving iron. Most previous methods for speciation of iron have been based on the calorimetric determination of Fe(II) followed by reduction of Fe(III) and analysis for total iron. The indirect determination of Fe(III) and the consumption of relatively large sample volumes have limited the accuracy and utility of such methods. A method based on ion-chromatography has been developed for simultaneous direct determination of Fe(II) and Fe(III). Sample pretreatment involves only conventional filtration and acidification. No interferences with the iron(II) determination were found; in determination of iron(III) the only interference observed was an artifact peak (of unknown origin) that occurred only when iron(II) was present, and had an area that was a function of the iron(II) concentration and could hence be corrected for. Solutions of iron(II) free from iron(III) can be prepared by treatment with a mixture of hydrogen and nitrogen in the presence of palladium black as catalyst, to reduce the iron(III). Photoreduction of iron(III) in acidified samples increases the Fe(II)/Fe(III) ratio; no means of circumventing this effect is known, other than storing the samples in the dark and analysing them as soon as possible.     

Adsorption of Ammonia and Sulfur Dioxide by Sorbents Based on Modified Montmorillonite

The sorption properties of montmorillonite modified with Fe(III) and Al(III) polyhydroxo complexes and with Fe(III)-Zr(IV), Fe(II)-Ni(II), and Fe(III)-Al(III) heteronuclear polyhydroxo complexes with respect to ammonia and sulfur dioxide were examined.     

Synthesis of two novel macroporous silica-based impregnated polymeric composites and their application in highly active liquid waste partitioning by extraction chromatography

Two kinds of novel macroporous silica-based chelating polymeric adsorption materials, TODGA/SiO2-P and CMPO/SiO2-P, were synthesized by impregnating and immobilizing two chelating agents, N,N,N',N'-tetraoctyl-3-oxapentane-1,5-diamide (TODGA) and octyl(phenyl)-N,N-diisobutylcarbamoylmethylphoshine oxide (CMPO), into the pores of SiO2-P particles. To separate minor actinides (MA(III)) such as Am(III) and Cm(III), the adsorption and elution of 13 typically simulated fission products from a 3 M HNO3 were performed. It was found that in the first column packed with TODGA/SiO2-P, all of the simulated elements were separated effectively into four groups: (1) Cs(I), Mo(VI), and the most portion of Ru(III) (non-adsorption group), (2) Sr(II), small portion of Gd(III) and all of light REs(III) (MA-lRE-Sr group), (3) most of Gd(III) and all heavy RE(III) (hRE group), and (4) Zr(IV), Pd(II), and a little of Ru(III) (Zr-Pd group) by eluting with 3.0 M HNO3, 1.0M HNO3, distilled water, and 0.5 M H2C2O4, respectively, at 298 K. MA(III) was predicted to flow into the second group along with Nd(III) because of their close adsorption-elution onto TODGA/SiO2-P. In the second column packed with CMPO/SiO2-P, MA-lRE-Sr group was separated into (1) Sr(II), (2) middle RE(III) such as Gd(III), Eu(III), Sm(III), and quite small portion of Nd(III) (MA-mRE), and (3) light RE(III) such as La(III), Ce(III), and most of Nd(III) by eluting with 3.0 M HNO3 and 0.05 M DTPA-pH 2.0, respectively, at 323 K. MA(III) was believed to flow into MA-mRE group along with Gd(III) due to their similar adsorption properties towards CMPO/SiO2-P. Based on positions of MA(III) appeared in light and heavy RE(III), an improved MAREC process for MA(III) partitioning from HLW was proposed.     

Monomeric and Trimeric Manganese(III) Complexes of 2-Hydroxy-5,10,15,20-tetraphenylporphyrin. Synthesis and Characterization

The hydrolysis of the monomeric five-coordinate (2-BzO-TPP)Mn(III)Cl complex has been investigated.(1) Evidence for the formation of the cyclic trimeric complex [(2-O-TPP)Mn(III)](3) is presented. The (1)H NMR spectroscopic evidence indicates that the trimeric manganese(III) complex has a head-to-tail cyclic trimeric structure with the pyrrolic alkoxide groups forming bridges from one macrocycle to the manganese(III) ion in the adjacent macrocycle PMn-O-PMn-O-PMn-O. The three manganese(III) porphyrin subunits are not equivalent. The characteristic upfield shift of the 3-H pyrrole resonance (-111.5 ppm at 291 K) was determined and considered as the diagnostic feature for the high-spin d(4) manganese(III)-pyrrole alkoxide coordination. The strong upfield shift of the 3-H resonance has been accounted for by the donation of the electron density from the filled orbital of the 2-O atom on the half-occupied d(z)()()2 orbital of the external manganese(III) ion. The other pyrrole resonances produce the complex multiplet at the typical -5 to -40 ppm region. The (1)H NMR spectra of the series of monomeric 2-substituted manganese(III) 5,10,15,20-tetraphenylporphyrin complexes (2-X-TPP)Mn(III)Cl have been obtained and analyzed. The pattern of the assigned seven pyrrole resonances reflects the asymmetry imposed by 2-substitution and has been used as a (1)H NMR spectroscopic probe to map the spin density distribution. The electronic effect is strongly localized at the beta-substituted pyrrole. The upfield shift of the 3-H resonance increases in the order (2-NO(2)-TPP)Mn(III)Cl < (2-BzO-TPP)Mn(III)Cl < (2-OCH(3)-TPP)Mn(III)Cl < (2-OH-TPP)Mn(III)Cl < (2-NH(2)-TPP)Mn(III)Cl < [(2-O-TPP)Mn(III)(OH)](-) following the increasing electron-donating properties of the beta-substituent.