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Synthesis, Structure, and Reactivity ofbis(1,2,4-tri-t-butylcyclopentadienyl) Complexes of Cerium

Description: The sterically demanding 1,2,4-tri-t-butylcyclopentadienylligand (1,2,4-(Me3C)3C5H2, hereafter Cp') has been used to preparemonomeric cerium metallocenes, Cp 2CeX (X = Cl, I, OSO2CF3), which areused to synthesize the benzyl, Cp'2CeCH2C6H5. The benzyl is a usefulstarting material for preparing other complexes in the Cp'2CeZ system (Z= BF4, F, NH2, C6H5, H). X-ray crystal structures of Cp'2CeOSO2CF3,Cp'2CeF, Cp'2CeCH2C6H5, and Cp'2CeH are presented. The benzyl slowlydecomposes in solution to toluene and a metallacycle,[Cp'][(Me3C)2C5H2(CMe2CH2)]Ce. The ring CMe3 groups of both themetallacycle and the hydride, Cp'2CeH, can be fully deuterated byprolonged exposure to C6D6, providing a useful labeling tool inmechanistic studies.The hydride activates C-F and/or C-H bonds influorobenzenes, C6HxF6-x , x = 0-5. The reactions are selective, with theselectivity depending on the presence of two fluorines ortho to thereaction site more than on the type of bond activated. Complexes of thetype Cp'2CeC6HxF5-x , x = 0-4, are formed as intermediates, which slowlydecompose in solution to Cp'2CeF and fluorobenzynes, C6HxF4-x, x = 0-4,which are trapped. The rate at which Cp'2CeC6HxF5-x complexes decomposeincreases as the number of fluorines decreases. Complexes with oneortho-fluorine decompose much faster than those with two ortho-fluorines.The metallacycle activates only C-H bonds in fluorobenzenes, permittingthe synthesis of specific Cp'2CeC6HxF5-x complexes. The crystal structureof Cp'2CeC6F5 is presented. The hydride and the metallacycle react withfluoromethanes, CH4-xFx, x = 1-3, through postulated Cp'2CeCH3-xFxintermediates to generate Cp'2CeF and other products. The other products,CH4, tri-t-butylbenzenes, tri-t-butylfluorobenzenes, and a presumedmetallocene cerium fluoride with one Cp' and one (Me2EtC)(Me3C)2C5H2ligand, suggest a decomposition pathway for Cp'2CeCH3-xFx , x = 1-3, thatinvolves carbenes or carbenoids, which are trapped. The hydridepolymerizes ethylene, but hydrogenates other olefins. The metallacycleactivates C-H bonds in olefins and aromatics to generate new complexeswith Ce-C bonds. The hydride reacts with one equivalent of CO in pentaneto generate (Cp'2Ce)2CH2O, whose crystal structure shows the presence ofa bridging dianionic formaldehyde ligand. (Cp'2Ce)2CH2O reacts H2 ...
Date: May 19, 2005
Creator: Werkema, Evan L.
Partner: UNT Libraries Government Documents Department

Bridging silyl groups in sigma-bond metathesis and [1, 2] shifts. An experimental and computational study of the reaction between cerium metallocenes and MeOSiMe3

Description: The reaction of Cp'2CeH (Cp' = 1,2,4-(Me3C)3C5H2 ) with MeOSiMe3 gives Cp'2CeOMe and HSiMe3 and the reaction of the metallacycle, Cp'[(Me3C)2C5H2C(Me) 2CH2]Ce, with MeOSiMe3 yields Cp'2CeOCH2SiMe3, formed from hypothetical Cp'2CeCH2OSiMe3 by a [1, 2] shift also known as a silyl-Wittig rearrangement. Although both cerium products are alkoxides, they are formed by different pathways. DFT calculations on the reaction of the model metallocene, Cp2CeH, and MeOSiMe3 show that the lowest energy pathway is a H for OMe exchange at Ce that occurs by way of a sigma-bond metathesis transition state as SiMe3 exchanges partners. The formation of Cp2CeOCH2SiMe3 occurs by way of a low activation barrier [1, 2]shift of the SiMe3 group in Cp2CeCH2OSiMe3. Calculations on a model metallacycle, Cp[C5H4C(Me)2CH2]Ce, show that the metallacycle favors CH bond activation over sigma-bond metathesis involving the transfer of the SiMe3 group in good agreement with experiment. The sigma-bond metathesis involving the transfer of SiMe3 and the [1, 2]shift of SiMe3 reactions have in common a pentacoordinate silicon at the transition states. A molecular orbital analysis illustrates the connection between these two Si-O bond cleavage reactions and traces the reason why they occur for a silyl but not for an alkyl group to the difference in energy required to form a pentacoordinate silicon or carbon atom in the transition state. This difference clearly distinguishes a silyl from an alkyl group as shown in the study of"Pyrolysis of Tetramethylsilane Yielding Free d-orbitals by Seyferth and Pudvin in ChemTech 1981, 11, 230-233".
Date: April 21, 2010
Creator: Werkema, Evan; Yahia, Ahmed; Maron, Laurent; Eisenstein, Odile & Andersen, Richard
Partner: UNT Libraries Government Documents Department

Cerium compounds as scintillators

Description: Stoichiometric Ce-materials with negligible Ce-Ce interactions should have superior scintillator properties. We present two materials: CeF{sub 3} and Ce{sub x}La{sub 1-x}P{sub 5}O{sub 14}. While cerium trifluoride is a known scintillator, pentaphosphate is of a limited usefulness, except as a remarkable model material. We show that quenching in fluoride is responsible for loss of 50% of the light output and is the cause of the, so-called, ultra fast component (2 ns). Light output of fluoride (about 50% of BGO) could be significantly improved. Deeper understanding of Ce-systems is needed to fully exploit their potentials. 10 figs., 6 refs.
Date: December 31, 1991
Creator: Wojtowicz, A. J.; Berman, E.; Koepke, C. & Lempicki, A.
Partner: UNT Libraries Government Documents Department

Many-body effects in heavy fermion compounds [sic]. Final technical report for period September 1984 - January 2001

Description: A theoretical investigation of many-body effects in Cerium and Uranium Heavy Fermion and Mixed Valent Compounds and their experimental manifestations in thermodynamic, transport, and spectroscopic properties is discussed in this report.
Date: May 1, 2002
Creator: Riseborough, Peter S.
Partner: UNT Libraries Government Documents Department

The Hanford Isotopes Production Plant Engineering Study

Description: Report presenting the conceptual design, estimates of capital and operating costs, and details of the operation of a plant "capable of high volume production of encapsulated heat sources" (p. 3) of radioisotopes Sr90, Cs137, Ce144, and Pm147.
Date: July 1963
Creator: La Riviere, J. R.; Michels, L. R.; Riches, H. C.; Rohrmann, C. A.; Smith, C. W. & Swift, W. H.
Partner: UNT Libraries Government Documents Department

Molecular Dynamics Simulations of the Structures of Europium Containing Silicate and Cerium Containing Aluminophosphate Glasses

Description: Rare earth ion doped glasses find applications in optical and photonic devices such as optical windows, laser, and optical amplifiers, and as model systems for immobilization of nuclear waste. Macroscopic properties of these materials, such as luminescence efficiency and phase stability, depend strongly on the atomic structure of these glasses. In this thesis, I have studied the atomic level structure of rare earth doped silicate and aluminophosphate glasses by using molecular dynamics simulations. Extensive comparisons with experimental diffraction and NMR data were made to validate the structure models. Insights on the local environments of rare earth ions and their clustering behaviors and their dependence on glass compositions have been obtained. In this thesis, MD simulations have been used to investigate the structure of Eu2O3-doped silica and sodium silicate glasses to understand the glass composition effect on the rare earth ions local environment and their clustering behaviors in the glass matrix, for compositions with low rare earth oxide concentration (~1mol%). It was found that Eu–O distances and coordination numbers were different in silica (2.19-2.22 Å and 4.6-4.8) from those in sodium silicate (2.32 Å and 5.8). High tendencies of Eu clustering and short Eu-Eu distances in the range 3.40-3.90 Å were observed in pure silica glasses as compared to those of silicate glasses with much better dispersed Eu3+ ions and lower probability to form clusters. The results show Eu3+ clustering behavior dependence on the system size and suggest for low doping levels, over 12,000 atoms to obtain statistical meaningful results on the local environment and clustering for rigid silica-based glasses. The structures of four cerium aluminophosphate glasses have also been studied using MD simulations for systems of about 13,000 atoms to investigate aluminum and cerium ion environment and their distribution. P5+ and Al3+ local structures were found stable while those of ...
Date: August 2012
Creator: Kokou, Leopold Lambert Yaovi
Partner: UNT Libraries

Selective separation of ultra-fine particles by magnetophoresis

Description: The selective and-specific extraction of species of interest fiom local environmental and other sample sources are importaut fbr scientific research, industrial processes, and environmental applications. A novel process for selective separation of ultrafine particles using 'magnetophoresis' is investigated. The principle of this process is that the direction and velocity of particle movement in a magnetic field are determined by magnetic, gravitational, and drag fbrces. By controlling these fbrces, one is able to control the migration rates of different species and then magnetically fiactionate mixtures of species into discrete groups. This study demonstrated for the fist time the selective separation of various species, such as iron (111) oxide, cupric (11) oxide, samarium (In) oxide, and cerium (III) oxide, by magnetophoresis. To better understand this phenomenon, a fbrce-balance model was developed that provides a good interpretation of the experimental results.
Date: January 1, 2002
Creator: Ying, T. (Tung-yu); Prenger, F. Coyne; Wingo, R. M. (Robert M.) & Worl, L. A. (Laura A.)
Partner: UNT Libraries Government Documents Department

Radiation Stability Studies

Description: From abstract: "An investigation of the radiation stabilities of aqueous solutions of sodium ethylenediamine tetraacetate and sodium acetate was made using a 3000-curie Co⁶⁰ source...A study of the behavior of the standard-size Beckman type glass pH electrodes in a solution containing 0.36 curie of Ce¹⁴⁴-Pr¹⁴⁴ activity per milliliter showed the useful electrode life to be of the order of two to eight days."
Date: September 22, 1952
Creator: Blanco, R. E.; Kibbey, A. H. & Pannell, J. H.
Partner: UNT Libraries Government Documents Department

Electrochemical synthesis of CeO2 and CeO2/montmorillonite nanocomposites.

Description: Nanocrystalline cerium oxide thin films on metal and semiconductor substrates have been fabricated with a novel electrodeposition approach - anodic oxidation. X-ray diffraction analysis indicated that as-produced cerium oxide films are characteristic face-centered cubic fluorite structure with 5 ~ 20 nm crystal sizes. X-ray photoelectron spectroscopy study probes the non-stoichiometry property of as-produced films. Raman spectroscopy and Scanning Electron Microscopy have been applied to analyze the films as well. Deposition mode, current density, reaction temperature and pH have also been investigated and the deposition condition has been optimized for preferred oriented film formation: galvanostatic deposition with current density of -0.06 mA/cm2, T > 50oC and 7 < pH < 10. Generally, potentiostatic deposition results in random structured cerium oxide films. Sintering of potentiostatic deposited cerium oxide films leads to crystal growth and reach nearly full density at 1100oC. It is demonstrated that in-air heating favors the 1:2 stoichiometry of CeO2. Nanocrystalline cerium oxide powders (4 ~ 10 nm) have been produced with anodic electrochemical synthesis. X-ray diffraction and Raman spectroscopy were employed to investigate lattice expansion phenomenon related to the nanoscale cerium oxide particles. The pH of reaction solution plays an important role in electrochemical synthesis of cerium oxide films and powder. Cyclic voltammetry and rotation disk electrode voltammetry have been used to study the reaction mechanisms. The results indicate that the film deposition and powder formation follow different reaction schemes. Ce(III)-L complexation is a reversible process, Ce3+ at medium basic pH region (7~10) is electrochemically oxidized to and then CeO2 film is deposited on the substrate. CE mechanism is suggested to be involved in the formation of films, free Ce3+ species is coordinated with OH- at high basic pH region (>10) to Ce2O3 immediately prior to electrochemically oxidation Ce2O3 to CeO2. CeO2 / montmorillonite nanocomposites were electrochemically produced. X-ray ...
Date: December 2003
Creator: Wang, Qi
Partner: UNT Libraries

Relationship between microstructure and efficiency of lithium silicate scintillating glasses: The effect of alkaline earths

Description: Lithium silicate glasses containing Ce{sup 3+} are known to be scintillators. Glasses in this family in which the Li is enriched ({sup 6}Li) are used as neutron detectors. The addition of Mg to this glass is known to increase the scintillation efficiency. We have found that substituting other alkaline earths results in a monotonic decrease of the scintillation efficiency with increasing atomic number. The total variation in scintillation efficiency from Mg to Ba is nearly a factor of 3. Prior experiments with this glass family show small differences in Raman and fluorescence spectra; evidence from thermoluminescence experiments indicates that the scintillation efficiency is most strongly correlated with structural effects in the neighborhood of the Ce{sup 3+} activator ion. The results of low-temperature studies of fluorescence and thermoluminescence of these glasses will be reported.
Date: May 1, 1995
Creator: Bliss, M.; Craig, R.A.; Sunberg, D.S. & Weber, M.J.
Partner: UNT Libraries Government Documents Department

Identification of the Charge Carriers in Cerium Phosphate Ceramics

Description: The total conductivity of Sr-doped cerium orthophosphate changes by nearly two orders of magnitude depending on the oxygen and hydrogen content of the atmosphere. The defect model for the system suggests that this is because the identity of the dominant charge carrier can change from electron holes to protons when the sample is in equilibrium with air vs. humidified hydrogen. In this work are presented some preliminary measurements that can help to clarify this exchange between carriers. The conduction behavior of a 2percent Sr-doped CePO4 sample under symmetric atmospheric conditions is investigated using several techniques, including AC impedance, H/D isotope effects, and chronoamperometry.
Date: June 2, 2010
Creator: Ray, Hannah L. & Jonghe, Lutgard C. De
Partner: UNT Libraries Government Documents Department


Description: Techniques to control the initial relative humidity over oxide/salt mixtures have been developed using cerium oxide as a surrogate for plutonium oxide. Such control is required to validate certain assumptions in the Department of Energy Standard DOE-STD-3013, and to provide essential information to support field surveillance at the storage sites for excess plutonium oxides. Concern over the validity of the assumption that corrosion induced degradation in 3013 containers could be controlled by assuring that the moisture content of any stored oxide/salt mixture was below 0.5 w t% arose when stress corrosion cracks were found in test samples exposed at room temperature to plutonium oxide/salt mixtures having a moisture content only marginally above 0.5 wt %. Additionally, analysis of the stress corrosion cracking observations suggests that the initial relative humidity over the oxide/salt mixture may play a major role in the cracking process. The investigations summarized in this report provide the procedures necessary to control the initial relative humidity to selected values within the range of 16 to 50% by controlling the loading relative humidity (18 to 60%) and the oxide/salt mixture water content (0.05 to 0.45 wt %). The studies also demonstrated that the initial relative humidity may be estimated by calculations using software EQ3/6. Cerium oxide/salt mixtures were used in this study because qualification tests with non-radioactive materials will reduce costs while increasing the breadth of the test programs required to support field surveillances of stored 3013 containers.
Date: August 1, 2011
Creator: Mickalonis, J. & Duffey, J.
Partner: UNT Libraries Government Documents Department

Cerium oxidation state in LSO:Ce scintillators

Description: Trivalent cerium ions form the luminescence centers in several important families of scintillation materials including the rare earth oxyorthosilicates, pyrosilicates, and aluminates. When comparing the experimentally determined scintillation properties of cerium-doped scintillators to theoretical models of scintillation mechanisms, there is often speculation regarding the fraction of the total cerium that exists in the radiative trivalent charge state (Ce{sup 3+}) rather than the non-radiative tetravalent state (Ce{sup 4+}). Until now, however, no technique has been developed to quantitatively measure both Ce{sup 3+} and Ce{sup 4+}. We report here for the first time direct measurements of Ce{sup 3+} and Ce{sup 4+} in Lu{sub 2}SiO{sub 5}:Ce scintillators. Synchrotron radiation was used to measure the x x-ray absorption on the M{sub 4} and M{sub 5} edges of Ce, and the results were compared to model samples of Ce{sup 3+} (Ce{sub 2}O{sub 3}) and Ce{sup 4+} (CeO{sub 2}) which provided clear signatures of the two charge states. The spectra were obtained with a high-resolution superconducting tunnel junction spectrometer on beamline 4.0.2 at the Advanced Light Source synchrotron at Lawrence Berkeley National Laboratory. The results clearly show 100% Ce{sup 3+}, independent of light yield and sample coloration. Therefore, energy migration to the luminescence centers appears to be the determining factor in the scintillation efficiency of these samples, rather than variations in the Ce{sup 3+}/Ce{sup 4+} ratio.
Date: October 13, 2004
Creator: Melcher, C L; Friedrich, S; Spurrier, M A; Szupryczynski, P & Nutt, R
Partner: UNT Libraries Government Documents Department