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Stereoselective Solid-State NaBH₄ Reduction of 1-Methylpentacyclo[5.4.0.0²,⁶.0³,¹⁰,0⁵,⁹]undecane-8, 11-Dione, Synthesis and Chemistry of Strained Alkenes, and Chemical and Microbial Synthesis of Racemic and Optically Active (S)-4-Hydroxy-2-Cyclohexenone

Description: Part I. Reduction of the 1-methylpentacyclo [5.4.0.0²,⁶.0³,¹⁰,0⁵,⁹]undecane-8, 11-dione (9) with solid NaBH₄ resulted in highly stereoselective reduction of both C=O groups in the substrate, thereby affording the corresponding endo-8, endo-11-diol (11a). The configuration of 11a was established unequivocally by converting 11a into the corresponding cyclic thiocarbonate ester, 12. Part II. Z-1,2-Di(1'-adamantyl)ethene (14) was synthesized with a high degree of stereoselectively in four steps (Sc… more
Date: August 1995
Creator: Xing, Dongxia
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Structural Elucidation of tert-Butyllithium/Lithium Alkoxide and Lithium Hydride/Lithium Alkoxide Mixed Aggregates

Description: The effects of lithium alkoxides on the rates of reactions and on the structures of a series of tert-butyllithium/lithium alkoxide mixed aggregates were studied, where the alkoxides were iso-butoxide, tert-butoxide and menthoxide. It was found that their effects depend not only on their amount present, but also on their steric bulk. The tert-butyllithium/lithium alkoxide mixed aggregates were exposed to UV light or heat to form lithium hydride/lithium alkoxide mixed aggregates. The aggregation… more
Date: December 1997
Creator: Nguyen, Hanh D.
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Surface and Interfacial Studies of Metal-Organic Chemical Vapor Deposition of Copper

Description: The nucleation and successful growth of copper (Cu) thin films on diffusion barrier/adhesion promoter substrates during metal-organic chemical vapor deposition (MOCVD) are strongly dependent on the initial Cu precursor-substrate chemistry and surface conditions such as organic contamination and oxidation. This research focuses on the interactions of bis(1,1,1,5,5,5-hexafluoroacetylacetonato)copper(II), [Cu(hfac)2], with polycrystalline tantalum (Ta) and polycrystalline as well as epitaxial tita… more
Date: December 1997
Creator: Nuesca, Guillermo M.
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FT-NMR and Raman Spectroscopic Studies of Molecular Dynamics in Liquids

Description: NMR relaxation and Raman lineshape analysis are well known methods for the study of molecular reorientational dynamics in liquids. The combination of these two methods provides another approach to tackle the characterization of molecular dynamics in liquids. Investigations presented here include (1) NMR relaxation study of polycyclic compounds in solution, (2) the study of nitromethane reorientational dynamics using the NMR and Raman methods, and (3) Raman lineshape analysis of reorientation he… more
Date: December 1993
Creator: Wang, Kuen-Shian
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Kinetic Studies of the Reactions of Alkyl and Silyl Hydrides

Description: The Kinetics of the reactions involving alkyl and silyl hydrides were studied by the flash photolysis / resonance fluorescence technique. The reactions of alkyl radicals (R = C₂H₅, i-C₃H₇, t-C₄H₉) with HBr have been studied at room temperature and the rate constants obtained (units are in cm³ s^-1 ) are: k₃.₃ = (7.01 ± 0.15) x 10^-12, k₃.₂ = (1.25 ± 0.06) x 10^-11, k₃.₁ = (2.67 ± 0.13) x 10^-11 These results, combined with previously determined reverse rate constants and other kinetic informati… more
Date: August 1996
Creator: Yuan, Jessie (Jessie Win-Jae)
open access

Selectivity Failure in the Chemical Vapor Deposition of Tungsten

Description: Tungsten metal is used as an electrical conductor in many modern microelectronic devices. One of the primary motivations for its use is that it can be deposited in thin films by chemical vapor deposition (CVD). CVD is a process whereby a thin film is deposited on a solid substrate by the reaction of a gas-phase molecular precursor. In the case of tungsten chemical vapor deposition (W-CVD) this precursor is commonly tungsten hexafluoride (WF6) which reacts with an appropriate reductant to yield … more
Date: August 1994
Creator: Cheek, Roger W. (Roger Warren)
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Part 1. Investigation of Aluminum Amino Acid Complexes; Part 2. Structural Studies of Aluminum Chalcogen Bonds

Description: Five different complexes of aluminum and amino acids have been synthesized and characterized. Reaction between aluminum halides and amino acids that do not contain either a carboxylate or a hydroxy group in the side chain produce complexes of the general formula, [Al(amino acid)_n(halide)_3-n]_m. The most prevalent form of this form of complex is where n = 2, and an example of this in which the halide is replaced by hydroxide ligand has been structurally characterized. The complex for which n =… more
Date: May 1996
Creator: Gravelle, Philip W. (Philip Wyn)
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Preparation and Stereochemistry of Reactive Intermediates Containing a Silicon-Carbon Double Bond

Description: 1,1-Dimethyl-2-neopentylsilene reacted with the N-methylimine of benzophenone to give 1,2,2-trimethyl-3- neopentyl-4,4-diphenyl-l-aza-2-silacyclobutane, I, and 2,3,4,4a-tetrahydro-2,3,3-trimethyl-1-phenyl-4-neopentyl-2- aza-3-silanephthalene, II, in 35% and 20% yields, respectively. Compounds I and II did not serve as thermal silene precursors. Heating I and II to over 280°C did not yield 1,3-disilacyclobutanes. In the presence of 2,3- dimethyl-1,3-butadiene typical silene products were not obt… more
Date: December 1991
Creator: Uang, Shinian
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Solvent and Ionic Complexes of the Calix[6]arenes

Description: One of the more attractive attributes of calixarenes is their wide variety of possible conformations and hence cavity shapes. However, the flexibility that allows this long-range benefit gives rise to major synthetic challenges when working with the larger members of the family. O-alkylations have proven to be the most widely employed synthetic routes to "functionalization" of the calixarenes, and these have shown a dependence upon both solvent and the metal ions present. Surprisingly, there ha… more
Date: December 1997
Creator: Wolfgong, William J.
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Part I: Solid State Studies of Larger Calixarenes : Part II: Synthesis and Characterization of Metallocalixarenes

Description: Calixarenes are a class of macrocyclic compounds that have garnered interest in large part because of their ability to form host-guest complexes with various types of molecules. For all of the studies of complex formation by calixarenes, most of the work to date has concentrated upon the smaller calixarenes, and little is understood about the relationship between the complexes formed when in solution and that observed in the solid state. The first part of the study, presented in Chapter 3, is o… more
Date: May 1998
Creator: Smith, Janna Marie
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NMR Study of the Reorientational and Exchange Dynamics of Organometallic Complexes

Description: Investigations presented here are (a) the study of reorientational dynamics and internal rotation in transition metal complexes by NMR relaxation experiments, and (b) the study of ligand exchange dynamics in transition metal complexes by exchange NMR experiments. The phenyl ring rotation in Ru3(CO)9(μ3-CO)(μ3-NPh) and Re(Co)2(CO)10(μ3- CPh) was monitored by 13C NMR relaxation experiments to probe intramolecular electronic and/or steric interactions. It was found that the rotation is relatively … more
Date: May 1996
Creator: Wang, Dongqing
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A Study of the Processing Properties of Hard-Particle Reinforced Composite Solders

Description: The microstructural, mechanical and thermal properties of various composite solder formulations were investigated. Special interest was given in observing the processing properties, microstructural characteristics, fatigue behavior, tensile strength, and the effect of environmental ageing on the composite solder formulations. The solderability parameters wetting and speed of soldering, reflow temperature, and the thermal stability of the resulting composite solder were also examined.
Date: May 1994
Creator: Calderon, Jose Guadalupe
open access

A Materials Approach to Silicon Wafer Level Contamination Issues from the Wet Clean Process

Description: Semiconductor devices are built using hyperpure silicon and very controlled levels of doping to create desired electrical properties. Contamination can alter these precisely controlled electrical properties that can render the device non-functional or unreliable. It is desirable to determine what impurities impact the device and control them. This study consists of four parts: a) determination of acceptable SCI (Standard Clean 1) bath contamination levels using VPD-DSE-GFAAS (Vapor Phase Decomp… more
Date: December 1996
Creator: Hall, Lindsey H. (Lindsey Harrison)
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Thermodynamic Properties of Nonelectrolyte Solutes in Ternary Solvent Mixtures

Description: The purpose of this dissertation is to investigate the thermodynamic properties of nonelectrolyte solutes dissolved in ternary solvent mixtures, and to develop mathematical expressions for predicting and describing that behavior in the solvent mixtures. Thirty-four ternary solvent systems were studied containing either alcohol (1-propanol, 2-propanol, 1-butanol, and 2-butanol), alkane (cyclohexane, heptane, and 2,2,4-trimethylpentane) or alkoxyalcohol (2-ethoxyethanol and 2-butoxyethanol) cosol… more
Date: August 1999
Creator: Deng, Tʻai-ho
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Experimental and Theoretical Studies of Polycarbocyclic Compounds

Description: Part I. Diels-Alder cycloadditions of 1,2,3,4,9,9-hexachloro-1α,4α,4aα,8aβ-tetrahydro-l,4-methanonaphthalene (32) and 1,2,3,4,9,9-hexachloro-lα,4α,6,7- tetrahydro-l,4-methanonaphthalene (33) to 4-methyl- and 4-phenyl-l,2,4-triazoline-3,5-dione [MTAD and PTAD, respectively] and to N-methylmaleimide (NMM) have been studied. The structures of several of the resulting cycloadducts were determined by X-ray crystallographic methods. The observed stereoselectivity of each of these Diels-Alder reaction… more
Date: May 1998
Creator: Shukla, Rajesh, 1964-
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Interactions of Clean and Sulfur-modified Reactive Metal Surfaces with Aqueous Vapor and Liquid Environments : A Combined Ultra-high Vacuum/electrochemistry Study

Description: The focus of this research is to explore the molecular-level interactions between reactive metal surfaces and aqueous environments by combined ultra-high vacuum/electrochemistry (UHV-EC) methodology. The objectives of this work are to understand (1) the effects of sulfate ions on the passivity of metal oxide/hydroxide surface layer, (2) the effects of sulfur-modification on the evolution of metal oxide/hydroxide surface layer, and (3) the effects of sulfur adsorbate on cation adsorption at meta… more
Date: May 1998
Creator: Lin, Tien-Chih, 1966-
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Ligand Substitution Studies in the Tetracobalt Cluster Co₄(CO)₁₀([mu]₄-PPh₂) and Synthesis and Reactivity Studies in the Fe₂Pt and FeCo₂ Mixed-metal Clusters

Description: The kinetics of ligand substitution for CO in Co4(CO)10(mu4-PPh2) , 1, have been investigated for the ligands P(OMe)3, P(OEt)3, PPh2H, P(0-i-Pr)3, P(n-Bu)3, PPh3, P(i-Pr)3, and PCy3 over a wide temperature range.
Date: August 1991
Creator: Don, Ming-jaw
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The Development of Predictive Models for the Acid Degradation of Chrysotile Asbestos

Description: The purpose of this study was to determine the factors affecting the acid degradation of chrysotile asbestos (Mg_3Si_2O_5(OH_4)) . Millions of tons of asbestos have found use in this country as insulative or ablative material. More than 95 percent of the asbestos in use is of the chrysotile variety. The remaining 5 percent is composed of various types of fibrous amphiboles. The inhalation of asbestos can lead to several diseases in humans. Asbestosis, lung cancer and mesothelioma are the most c… more
Date: May 1993
Creator: Ingram, Kevin D. (Kevin Dean)
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Spectrofluorometric and Solubility Studies of Polycyclic Aromatic Hydrocarbons in Hydrogen Bonded Binary Solvent Mixtures

Description: The purpose of this dissertation is to investigate the behavior of polycyclic aromatic hydrocarbons (PAHs) in binary solvent systems and determine and/or develop predictive mathematical expressions for describing solutions in which hydrogen-bonding occurs.
Date: May 1997
Creator: Powell, Joyce R., 1968-
open access

Solution Studies of the Structures and Stability of Mixed Lithium Alkoxide/Alkvllithium Aggregates

Description: New one- and two-dimensional NMR techniques were used to elucidate the solution structures of these complex mixtures. The system, lithium tert-butoxide/tert-butyllithium, was studied as a model system with O/Li ratios varying from 0/1 to 1/1. It was found that at low O/Li ratios, a single mixed tetrameric aggregate was formed. At higher O/Li ratios, mixed hexameric species were formed. Two other systems, lithium isopropoxide/iso-propyllithium and lithium n-propoxide/n-propyllithium were also st… more
Date: December 1992
Creator: DeLong, George T. (George Thomas)
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