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At least 325 records · Page 18Linked to original sources
PubMed2006

A general one-pot synthesis for elusive 2-substituted indenes: does bis[2-(tert-butyl)indenyl]zirconium(IV) dichloride/MAO polymerise ethene?

Among the 2-substituted indenes, 2-trifluoroindene and 2-tert-butylindene are poorly or incompletely described in the open literature. We herein describe an efficient one-pot synthesis of these compounds as a variation of the Perkin reaction which allows us to refute an earlier claim that bis(2-tert-butylindenyl)zirconium(IV) dichloride (2a) will not polymerise ethene. In fact, 2a/MAO polymerises ethene to extremely high molecular weights. Extensive DFT calculations on the polymerisation mechanism revealed an unprecedented suppression of the otherwise predominant chain termination by beta-hydride transfer due to steric congestion of the active site.

Journal Article↗
PubMed2006

Dynamics of D2 released from the dissociation of D2O on a zirconium surface.

Hydrogen is efficiently released during water dissociation on zirconium (Zr), while even very rapid temperature programmed heating of a hydrogen covered Zr surface predominantly leads to dissolution (approximately 99% dissolution). To help resolve these apparently contradictory observations, we have studied the dynamics of water (D2O) dissociation on a crystalline Zr surface by probing the rotational and vibrational energy distributions of the D2 produced using resonant enhanced multiphoton ionization spectroscopy. The internal-state energy distribution of the D2 product was found to be rotationally cold and vibrationally hot with respect to the temperature of the surface. The rotational distribution shows slight deviations from Boltzmann's law, with a mean rotational temperature of 426 K while the surface is at 800 K. The population of the nu"=1 vibration is at least four times higher than a 800 K temperature would allow, this corresponding to a vibrational temperature of 1100 K. Information on the translational energy of the D2 product have also been obtained by time-of-flight spectroscopy and it is found to be nearly thermally equilibrated with the surface temperature. Similar results were obtained from studies of D2 scattered from a clean Zr surface, and of D2 released by a slow thermal desorption process which involves dissolved hydrogen as the source. The reconciliation of the present results with those for thermal desorption of preadsorbed hydrogen implies a role for both surface and subsurface adsorption sites on the Zr surface and clearly demonstrates that at high temperatures, the release of D2 arises from the recombinative desorption of adsorbed hydrogen formed by the complete dissociation of D2O.

Journal Article↗
PubMed2006

Ansa-metallocene polymerization catalysts derived from [2+2]cycloaddition reactions of bis(1-methylethenyl-cyclopentadienyl)zirconium systems.

Bis(1-methylethenyl-cyclopentadienyl)zirconium dichloride (7a) was prepared by a fulvene route. Photolysis at 0 degrees C with Pyrex-filtered UV light resulted in a rapid and complete intramolecular [2+2]cycloaddition reaction to yield the corresponding cyclobutylene-bridged ansa-zirconocene dichloride isomer (8a). This is one of the rare examples of an organic functional group chemistry that leads to carbon-carbon coupling at the framework of an intact sensitive group 4 bent metallocene complex. More sterically hindered open metallocenes that bear bulky isopropyl or tert-butyl substituents at their Cp rings in addition to the active 1-methylethenyl functional group undergo the photochemical ansa-metallocene ring closure reaction equally facile. The metallocene systems used and obtained in this study have served as transition metal components for the generation of active metallocene propene polymerization catalysts.

Journal Article↗
PubMed2004

High radioactive concentration of 99mTc from a zirconium [99Mo]molybdate gel generator using an acidic alumina column for purification and concentration.

BACKGROUND: Newer applications of radiopharmaceuticals in nuclear medicine require pertechnetate of moderate to high radioactive concentration. Hence there is a need to develop simple procedures for the concentration of pertechnetate, and such a procedure is given in this paper. METHODS: Ten to 20 ml of sodium [Tc]pertechnetate eluted in de-ionized water from a zirconium [Mo]molybdate (ZrMo) gel column generator was passed through 2 g of an acidic alumina bed (35 x 8 mm) in order to remove the co-eluted traces of Mo and to retain the pertechnetate. The retained pertechnetate was then re-eluted, quantitatively, in 3 ml of normal saline, from the alumina column. RESULTS: About a 4-fold increase in radioactive concentration of Tc was obtained (cf. approximately 10-12 ml normal saline is required for the elution of Tc from the gel column). Generators containing up to 22.2 GBq (600 mCi) Mo in 6-7 g ZrMo gel column (35 x 13 mm) were prepared and a radioactive concentration of Tc up to 4 GBq x ml (110 mCi x ml) was obtained on the first day of use. The overall recovery of Tc was >90%, Mo breakthrough was 10 to 10% and the duration of concentration was 3-5 min. The chemical impurity in terms of Al, Mo and Zr was <10 ppm each. The same procedure for the concentration of pertechnetate was applied to generators with 12-15 g ZrMo gel beds to obtain a higher capacity Tc gel generator, with similar findings.

Aluminum Oxide↗
PubMed2003

Local order of liquid and supercooled zirconium by ab initio molecular dynamics.

It has been suggested that icosahedral short-range order (SRO) occurs in deeply undercooled melts of pure metallic elements. We report results of first-principles molecular dynamics simulations for stable and undercooled zirconium liquids. Our results emphasize the occurrence of a local order more complex than the icosahedral one. For stable liquid, the local order is interpreted on the basis of a competition between a polytetrahedral SRO and a bcc-type SRO. We also demonstrate that a bcc-type SRO increases with the degree of undercooling.

Journal Article↗
PubMed2004

Monocrystal elastic constants of the negative-thermal-expansion compound zirconium tungstate (ZrW2O8).

We measured zirconium tungstate's elastic constants C(ij). This compound shows relatively soft, nearly isotropic elastic constants with normal Poisson ratios and no approach to Born instability. ZrW2O8 shows normal ambient-temperature elastic constants C(ij), but remarkable dC(ij)/dT that show dominant low-frequency acoustic-vibration modes. From the bulk modulus, we estimated the total ambient-temperature thermodynamic Grüneisen parameter as gamma = -1.2. The dB/dT slope gives a Grüneisen parameter gamma = -7. The 300-0 K bulk-modulus increase (40%) seems unprecedented and breaks Birch's law of corresponding states.

Journal Article↗
PubMed2000

Tribenzyl{eta(5)-[2-(p-tolyl)prop-2-yl]cyclopentadienyl}zirconium.

The title compound, [Zr(C(7)H(7))(3)(C(15)H(17))], (I), crystallizes from light petroleum with two independent molecules in the asymmetric unit. Whereas in the parent molecule, Zr(eta(5)-C(5)H(5))(CH(2)Ph)(3), all three Zr-CH(2)Ph angles are equal, in (I), they differ significantly. In spite of their different environments, both independent molecules in (I) exhibit a small, an expected, and a large Zr-CH(2)Ph angle. The angles are similar to those of the closely related tribenzyl[eta(5)-(benzyldimethylsilyl)cyclopentadienyl]zirconium complex. The smallest Zr-CH(2)Ph angle and the consequently relatively short Zr.C(ipso) distance are indicative of eta(2)-bonding of the benzyl group.

Journal Article↗
PubMed2003

A novel zirconium polyoxometalate compound: (NH(4))(9)[Zr(2)(mu-OH)(H(2)O)(2)(AsOH)(2)(AsW(7)O(28))(AsW(10)O(36))].26H(2)O.

The crystal structure of the title compound, nonaammonium (arsenic decatungstido)(arsenic heptatungstido)diaqua-mu-hydroxo-(hydroxyarsenido)dizirconium hexacosahydrate, which was obtained from the reaction of [NaAs(4)W(40)O(140)](27-) with Zr(IV), has been determined. The anionic complex consists of two hydroxyl-bridged seven-coordinate capped trigonal-prismatic zirconium ions, which are bonded to an [AsW(10)O(36)](9-) anion and to an [AsW(7)O(28)](11-) anion that has two [AsOH](2+) capping units. The asymmetric unit contains half of the complex, with one crystallographically independent Zr atom. Crystallographic m symmetry imposed by the monoclinic C2/m space group gives rise to the asymmetric unit comprising half of the complex with one crystallographically independent Zr atom.

Journal Article↗
PubMed2003

A zirconium zwitterion containing a caged amine H atom.

The crystallographically centrosymmetric zwitterion bis[tris(3,5-dimethyl-2-oxidobenzyl-kappaO)ammonium]zirconium(IV) crystallizes as the chloroform disolvate, [Zr(C(27)H(31)NO(3))(2)].2CHCl(3), with the two molecules of chloroform closely associated with two of the aromatic rings. The Zr atom has a distorted octahedral geometry with three phenoxy O atoms from each of the two ligands coordinated to it. Charge balance is maintained by protonation of each N atom, which then forms intramolecular hydrogen-bonding interactions to all three adjacent O atoms.

Journal Article↗
PubMed2004

A fluorophenylboron-functionalized zirconium silsesquioxane complex.

Bis(eta5-cyclopentadienyl)[rel-(1R,5S,7R,14S)-(1,3,5,7,9,11,14-heptacyclopentyl-7,14-dioxidotricyclo[7.3.3(1,9).1(5,11)]heptasiloxan-3-yloxy)bis(pentafluorophenyl)borane2-]zirconium, [Zr(C5H5)2(C47H63BF10O12Si7)], consists of [ZrCp2] (Cp is cyclopentadienyl) and [(C6F5)2B] moieties bound to a silsesquioxane core. The silsesquioxane binds to the Zr atom through two of its O atoms to form a distorted tetrahedron. The [(C6F5)2B] moiety is bound to the silsesquioxane through an O atom, forming an Si-O-B bond angle of 168.4 (4) degrees. The steric and electronic effects of the Zr atom and the borate moieties force the silsesquioxane core to distort. These distortions can be seen by examination of the Si-O-Si bond angles.

Journal Article↗
PubMed2005

Atomic interactions in ethylenebis(1-indenyl)zirconium dichloride as derived by experimental electron density analysis.

A topological analysis of the experimental electron density in racemic ethylenebis(1-indenyl)zirconium dichloride, C20H16Cl2Zr, measured at 100 (1) K, has been performed. The atomic charges calculated by the numerical integration of the electron density over the zero-flux atomic basins demonstrate the charge transfer of 2.25 e from the Zr atom to the two indenyl ligands (0.19 e to each) and two Cl atoms (0.93 e to each). All the atomic interactions were quantitatively characterized in terms of the electron density and the electronic energy-density features at the bond critical points. The Zr-C2 bond paths significantly curved towards the C1-C2 bond were found; no other bond paths connecting the Zr atom and indenyl ligand were located. At the same time, the pi-electrons of the C1-C2 bond are significantly involved in the metal-ligand interaction. The electron density features indicate that the indenyl coordination can be approximately described as eta1 with slippage towards eta2. The ;ligand-opposed' charge concentrations around the Zr atom were revealed using the Laplacian of the electron density and the one-particle potential; they were linked to the orbital representations. Bonds in the indenyl ligand were characterized using the Cioslowski-Mixon bond-order indices calculated directly from the experimental electron density.

Journal Article↗
PubMed2006

Structures and the oxygen deficiency of tetragonal and monoclinic zirconium oxide nanoparticles.

The crystal structure of zirconium oxide nanoparticles was refined by the Rietveld analysis of synchrotron X-ray powder diffraction data measured at 298 K. In the nanoparticles, two phases of tetragonal ZrO(2 - delta) (average particle size: 11 +/- 2 nm) and monoclinic ZrO2 (average particle size: 24 +/- 4 nm) existed, where the weight fractions were estimated to be 84.9 and 15.1 wt%, respectively. The structural refinement suggests that the tetragonal ZrO(2 - delta) has an oxygen deficiency [delta = 0.031 (7)] and that the monoclinic ZrO(2 - delta) has less oxygen deficiency (delta approximately 0), where delta is the vacancy concentration. The monoclinic ZrO2 has a larger unit-cell volume. The maximum-entropy method analysis indicated covalent bonding between Zr and O atoms.

Journal Article↗
PubMed2002

Niobium-zirconium chronometry and early solar system development.

Niobium-92 (92Nb) decays to zirconium-92 (92Zr) with a half-life of 36 million years and can be used to place constraints on the site of p-process nucleosynthesis and the timing of early solar system processes. Recent results have suggested that the initial 92Nb/93Nb of the solar system was high (>10(-3)). We report Nb-Zr internal isochrons for the ordinary chondrite Estacado (H6) and a clast of the mesosiderite Vaca Muerta, both of which define an initial 92Nb/93Nb ratio of approximately 10(-5). Therefore, the solar system appears to have started with a ratio of <3 x 10(-5), which implies that Earth's initial differentiation need not have been as protracted as recently suggested.

Journal Article↗
PubMed1997

Compressibility, Phase Transitions, and Oxygen Migration in Zirconium Tungstate, ZrW2O8

In situ neutron diffraction experiments show that at pressures above 2 kilobars, cubic zirconium tungstate (ZrW2O8) undergoes a quenchable phase transition to an orthorhombic phase, the structure of which has been solved from powder diffraction data. This phase transition can be reversed by heating at 393 kelvin and 1 atmosphere and involves the migration of oxygen atoms in the lattice. The high-pressure phase shows negative thermal expansion from 20 to 300 kelvin. The relative thermal expansion and compressibilities of the cubic and orthorhombic forms can be explained in terms of the "cross-bracing" between polyhedra that occurs as a result of the phase transition.

Journal Article↗
PubMed2000

Zirconium phosphonate/1,4,5,8-naphthalenediimides self-assembled films

The formation and characterization of self-assembled films of zirconium phosphonate/N,N'-di(2-phosphonoethyl)-1,4,5,8-naphthalenediimide (DPN) is presented. The films were produced on glass substrates by deposition of alternating layers of Zr+4 and DPN. Films containing up to 16 layers on each side of the substrate were obtained and monitored by absorption spectroscopy and ellipsometry. When irradiated, the initially colorless films turned to a persistent pinky color reminiscent of that of DPN anion radical. These films are a promising material to the development of photovoltaic devices.

Journal Article↗
PubMed2004

Liquid-liquid extraction of tetravalent zirconium from acidic chloride solutions using Cyanex 272.

The liquid-liquid extraction of zirconium(IV) from acidic chloride solutions was carried out with Cyanex 272 as an extractant diluted in kerosene. An increase of the acid concentration decreased the percentage extraction of metal, which indicates that the extraction follows ion exchange-type mechanism: MO2+(aq) + 2(HA)2(org) <--> MO (HA2)2(org) + 2H+(aq), where, M = Zr(IV); HA = Cyanex 272. The extraction of Zr(IV) increases with an increase of the extractant concentration. In a plot of log D vs. log[extractant], M is linear with a slope of approximately 2, indicating the association of two moles of extractant with the extracted metal species. On the other hand, the extraction decreases with an increase of the H+ ion concentration. A plot of log D vs. log[H+] gave a straight line with a negative slope of 1.7, indicating the exchange of two moles of hydrogen ions for every mole of Zr(IV). The effect of the Cl- ion concentration at a constant concentration of [H+] did not show any change in the D values. The addition of sodium salts enhanced the percentage extraction of metal, and followed the order of NaSCN > NaNO3 > Na2SO4 > NaCl. The stripping of metal from the loaded organic (L.O) with different acids indicated sulfuric acid to be the best stripping agent. An increase of the temperature during the extraction and stripping stages increases the metal transfer, showing that the process is exothermic. The synergism, regeneration and recycling capacity of Cyanex 272; the extraction behavior of associated elements, such as Hf(IV), Ti(IV), Al(III), Fe(III); and IR spectra of the extracted Zr-Cyanex 272 complex were studied.

Journal Article↗
PubMedDate not supplied

Effect of surface treatments on the resin bond to zirconium-based ceramic.

PURPOSE: This study tested the hypothesis that the tribochemical silica coating on ceramic surfaces increases the bond strength of resin cement to a glass-infiltrated zirconium-based ceramic. MATERIALS AND METHODS: Fifteen blocks of In-Ceram Zirconia from CEREC InLab (5 per group) and 15 composite blocks (Z-250) 5 mm x 5 mm x 4 mm were made. The ceramic surfaces were polished, and the blocks were divided into three groups: (1) airborne abrasion with 110-microm aluminum oxide particles; (2) Rocatec system, tribochemical silica coating; and (3) CoJet system, tribochemical silica coating. The ceramic blocks were cemented to the composite blocks using Panavia F according to the manufacturer's specifications. All samples were stored in 37 degrees C distilled water for 7 days and later sectioned in two axes using a diamond disk under cooling to obtain specimens with a cross-sectional area of approximately 1 mm2 (n = 45). Each specimen was then attached with cyanoacrylate glue to an adapted device for the microtensile test, which was carried out on a universal testing machine. RESULTS: The results were subjected to ANOVA and Tukey's test. Group 2 (23.0+/-6.7 MPa) and group 3 (26.8+/-7.4 MPa) showed greater bond strength than group 1 (15.1+/-5.3 MPa). There was no significant difference between groups 2 and 3. All failures were in the adhesive zone. CONCLUSION: The hypothesis was confirmed--the tribochemical systems increased the bond strength between Panavia F and In-Ceram Zirconia.

Air Abrasion, Dental↗
PubMed1997

[Quantitative determination of the nickel, tin, copper, scandium, zirconium and hafnium in silicate sample by laser microspectrochemical analysis].

Quantitative determination of the nickel, tin, copper, scandium, zirconium and hafnium in silicate sample were carried out by laser microspectrochemical analysis, results show that the method has good precision and accuracy. The stability of the laser output and the selection of auxiliary spark excitation condition in experimental process were discussed.

English Abstract↗