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Application of tracer packet technique for multielemental uptake studies on the inorganic ion exchanger zirconium vanadate.

The conception of tracer packet was first started with the irradiation of a thick cobalt target with 16O, 7Li and 12C beams, consecutively. This produced carrier-free radiotracers of Mn, Cu, Zn, Ga, Ge, As and Se. These elements are adjacent members in the periodic table and are of nutritional importance. Another 'tracer packet', which was subsequently designed, was of heavy and toxic metals. A gold target irradiated with medium energy 7Li and 12C produced 197Hg, 200Tl, 200Pb, 204Bi, 204Po. The uptake of these elements has been studied using two different ion exchangers, one of inorganic origin and the other of chelating type.

Hydrogen-Ion Concentration↗

Synthesis, characterization, and X-ray crystal structure of a gallium monohydroxide and a hetero-bimetallic gallium zirconium oxide.

A monomeric hydroxide of gallium, LGa(Me)OH, containing terminal hydroxide and methyl groups was prepared by the hydrolysis of LGa(Me)Cl in the presence of N-heterocyclic carbene and water [L = HC{(CMe)(2,6-i-Pr2C6H3N)}2] in high yield and in a pure form. LGa(Me)OH was used as a synthon to assemble the first hetero-bimetallic compound with a Ga-O-Zr core, [(LGaMe)(Cp2ZrMe)](mu-O).

Crystallography, X-Ray↗

Epoxide-opening and group-transfer reactions mediated by monomeric zirconium imido complexes.

N-tert-Butylimidozirconocene (Cp2Zr=Nt-Bu) and its analogue (ebthi)Zr=NAr (ebthi = ethylenebis(tetrahydroindenyl), Ar = 2,6-dimethylphenyl) undergo overall cycloaddition reactions at ambient temperature with epoxides that lack accessible beta-hydrogens. The process results in addition of the Zr=N bond to an epoxide C-O bond, leading to azazirconacyclopentanes. The regio- and stereochemistry of the products implicate a stepwise mechanism, with the intermediacy of zwitterions having substantial carbocation character at the substituted carbon of the ring-opened epoxide-derived fragment. The azametallacycles undergo facile cleavage to beta-amino alcohols upon addition of mild acid.

Crystallography, X-Ray↗

Extraction of zirconium nitrate by TBP in n-octane: influence of cation type on third phase formation according to the "sticky spheres" model.

Small-angle neutron scattering (SANS) data for the tri-n-butyl phosphate (TBP)-n-octane, HNO(3)-Zr(NO(3))(4) solvent extraction system, obtained under a variety of experimental conditions, have been interpreted using the Baxter model for hard spheres with surface adhesion. The increase in scattering intensity in the low Q range observed when increasing amounts of Zr(NO(3))(4) were extracted into the organic phase was interpreted as arising from interactions between small reverse micelle-like particles containing two to three TBP molecules. Upon extraction of Zr(NO(3))(4), the particles interact through attractive forces between their polar cores with a potential energy that exceeds 2 k(B)T. The interparticle attraction, under suitable conditions, leads to third phase formation. A linear relationship exists between the derivative of the potential energy of attraction with respect to the concentration of nitrate ions in the organic phase and the ionization potential or the hydration enthalpy of the extracted metal cations.

Cations↗

Adsorption and removal of oxo-anions of arsenic and selenium on the zirconium(IV) loaded polymer resin functionalized with diethylenetriamine-N,N,N',N'-polyacetic acid.

A polymer adsorbent in which a Zr(IV)-edta complex analogue is immobilized has been prepared and applied to the removal of oxo-anions of As(III), As(V) and Se(IV). Effective retention of these anions has been demonstrated with the proposed polymer complex system. The adsorption mechanism of oxo-anions onto the Zr(IV)-chelated polymer complex has been investigated using Zr(IV)-edta as the model compound. The formation of mixed complexes with oxo-anions has been exemplified by the isolation of the carbonato complex K2[Zr(CO3)edta].3H2O, the structure of which has been confirmed by X-ray crystallography. NMR study suggests that oxo-anions that form weak or moderate conjugate acids, including those of As(III), As(V) and Se(IV), can form mixed complexes with Zr(IV)-edta using the unsaturated coordination site. However, oxo-anions of strong conjugate acids did not show any appreciable interaction with this complex. According to these observations, retention of oxo-anions on the Zr(IV)-chelated polymer complex has been interpreted by a ligand substitution reaction. The adsorption characteristics of As(III), As(V) and Se(IV) on the Zr(IV)-loaded resin have been examined with respect to the equilibrium adsorption, percentage extraction and the effect of co-existing ions. The adsorption and desorption cycles of the oxo-anions have been demonstrated using a column packed with the proposed resin without any loss of column performance, which indicates the possibility for repeated use.

Acetic Acid↗

A new synthetic entry to phosphinophosphinidene complexes. Synthesis and structural characterisation of the first side-on bonded and the first terminally bonded phosphinophosphinidene zirconium complexes [mu-(1,2:2-eta-tBu2P=P)[Zr(Cl)Cp2]2] and [[Zr(PPhMe2)Cp2](eta1)-P-PtBu2)].

The reactions of lithiated diphosphanes with transition metal chlorides constitute a new general entry to phosphinophosphinidene complexes: the reaction of Cp2ZrCl2(Cp = C5H5) with tBu2P-P(SiMe3)Li (molar ratio approximately 1:1) yields [mu-(1,2:2-eta-tBu2P=P)[Zr(Cl)Cp2]2]; the reaction of Cp2ZrCl2 with tBu2P-P(SiMe3)Li (molar ratio approximately 1:2) and an excess of PPhMe2 in DME yields the first terminally bonded phosphinophosphinidene complex, [[Zr(PPhMe2)Cp2](eta1-P-PtBu2)].

Crystallography, X-Ray↗