Thermolysis of CoRu(CO)7(m -PPh2) (1) in refluxing 1,2-dichloroethane in the presence of the diphosphine ligands 2,3-bis(diphenylphosphino)maleic anhydride (bma) and 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd) furnishes the new mixed-metal complexes CoRu(CO)4(μ -P-P)(μ -PPh2) [where P-P = bma (3); bpcd (6)], along with trace amounts of the known complex CoRu(CO)6(PPh3)(μ -PPh2) (4). The requisite pentacarbonyl intermediates CoRu(CO)5(μ -P-P)(μ -PPh2) [where P-P = bma (2); bpcd (5)] have been prepared by separate routes and studied for their conversion to CoRu(CO)4(μ -P-P)(μ -PPh2). The complexes 2/3 and 5/6 have been isolated and fully characterized in solution by IR and NMR spectroscopy. The kinetics for the conversion of 2→3 and of 5→6 were measured by IR spectroscopy in chlorobenzene solvent. On the basis of the first-order rate constants, CO inhibition, and the activation parameters, a mechanism involving dissociative CO loss as the rate-limiting step is proposed. The solid-state structure of CoRu(CO)4(μ -bma)(μ -PPh2) (3) reveals that the two PPh2 groups are bound to the ruthenium center while the maleic anhydride π bond is coordinated to the cobalt atom. Thermolysis of the cluster Ru3(CO)12 with the bis(phosphine)hydrazine ligand (MeO)2PN(Me)N(Me)P(OMe)2 (dmpdmh) in toluene at 75°C furnishes the known clusters Ru4(CO)12[μ -N(Me)N(Me)] (9) and Ru3(CO)11[P(OMe)3] (10), in addition to the new …

Dimethoxynaphthalene (donor) and quinone (acceptor) have been chosen as a suitable redox pair and are bonded to either permethylated silane chains or corresponding permethylated alkyl chains to form Acceptor-(Bridge)-Donor molecules. The idea that the s-delocalization phenomenon of silane chains may greatly facilitate ET reactions will be tested. The starting material for the donor precursor, 4-(1,4-dimethoxynaphthyl)bromocyclohexane, was 1,4-naphthoquinone. After methylation and bromination, the Grignard reagent of the resulting bromide was reacted with cyclohexanedione, mono ethylene ketal. The resulting alcohol was changed to the donor precursor through the following functional group transformation steps: dehydration, hydrogenation, deketalization and bromination. 1,4-Dibenzyloxybromobenzene, the precursor for the acceptor, was synthesized from 1,4-hydroquinone through bromination and benzylation. The connection of the two precursors and either permethylated silane chains or permethylated alkyl chains will give the final target molecules for ET research. Progress on this is included.

The second order rate constants for nucleophilic substitution by methoxide of (Z)- and (E)-O-methylbenzohydroximoyl fluorides [C6H4C(F)=NOCH3] with various substituents on the phenyl ring [p-OCH3 (1h, 2h), p-CH3 (1g, 2g), p-Cl (1f, 2f), p-H (1e, 2e), (3,5)-bis-CF3 (1i, 2i)] in 90:10 DMSO:MeOH have been measured. A Hammett plot of these rate constants vs σ values gave positive ρ values of 2.95 (Z isomer) and 3.29 (E isomer). Comparison of these rates with methoxide substitution rates for Omethylbenzohydroximoyl bromide [C6H4C(Br)=NOCH3] and Omethylbenzohydroximoyl chloride [C6H4C(Cl)=NOCH3] reveal an element effect for the Z isomers of Br:Cl:F(1e) = 2.21:1.00:79.7 and for the E isomers of Cl:F(2e) = 1.00:18.3. With the p-OCH3-imidoyl halides the following element effects are found: Br:Cl:F(1h) = 2.78:1.00:73.1 for the Z isomer and Br:Cl:F(2h) = 1.97:1.00:12.1 for the E isomer. Measurement of activation parameters revealed ∆S≠ = -17 eu for 1e and ∆S≠ = -9.9 eu for 2e. Ab initio calculations (HF/6-31+G*, MP2/6-31+G*//HF/6-31+G*, B3LYP/6- 31+G*//HF/6-31+G*, HF-SCIPCM/6-31+G*//HF/6-31+G*) were performed to define the reaction surface. These calculations demonstrate a relatively large barrier for nucleophilic attack in relation to halogen loss and support the experimental findings that this reaction proceeds by an addition-elimination mechanism (AN# + DN). The imidoyl fluorides have been used to synthesize …

The reaction between the tetrahedrane cluster RCCo3(CO)9{R = CHO (1), H (3)} and the redox-active diphosphine ligand 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3- dione (bpcd) leads to the replacement of two CO groups and formation of RCCo3(CO)7(bpcd) {R = CHO (2), H (4)}. Clusters 2 and 4 are thermally unstable and readily transform into the new P-C bond cleavage cluster 5. All three clusters 2, 4, and 5 have been isolated and fully characterized in solution by IR and 31P NMR spectroscopy. VT 31P NMR data indicate that the bpcd ligand in RCCo3(CO)7(bpcd) is fluxional at 187 K in THF. Clusters 2, 4, and 5 have been structurally characterized by X-ray diffraction analyses.

Metal and oxide interactions are of broad scientific and technological interest in areas such as heterogeneous catalysis, microelectronics, composite materials, and corrosion. In the real world, such interactions are often complicated by the presence of interfacial impurities and/or high electric fields that may change the thermodynamic and kinetic behaviors of the metal/oxide interfaces. This research includes: (1) the surface hydroxylation effects on the aluminum oxide interactions with copper adlayers, and (2) effects of high electric fields on the interface of thin aluminum oxide films and Ni3Al substrate. X-ray photoelectron spectroscopy (XPS) studies and first principles calculations have been carried out to compare copper adsorption on heavily hydroxylated a- Al2O3(0001) with dehydroxylated surfaces produced by Argon ion sputtering followed by annealing in oxygen. For a heavily hydroxylated surface with OH coverage of 0.47 monolayer (ML), sputter deposition of copper at 300 K results in a maximum Cu(I) coverage of ~0.35 ML, in agreement with theoretical predictions. Maximum Cu(I) coverage at 300 K decreases with decreasing surface hydroxylation. Exposure of a partially dehydroxylated a-Al2O3(0001) surface to either air or 2 Torr water vapor results in recovery of surface hydroxylation, which in turn increases the maximum Cu(I) coverage. The ability of surface hydroxyl …

A 1H, 13C, and 6Li NMR study of 2-ethylhexyllithium showed that 2- ethylhexyllithium exists solely as a hexamer in cyclopentane solution over the temperature range from 25 to -65 °C. Furthermore, 2-ethylhexyllithium and lithium 2- ethyl-1-hexoxide were shown to form mixed aggregates when the alkoxide was formed in situ by reacting 2-ethylhexyllithium with 2-ethyl-1-hexanol. A multinuclear, variable temperature NMR study of a sample with an O:Li ratio of 0.2 led to the identification of at least four such aggregates, one of which was found to be a hexamer with the composition R5(RO)Li6. Studies of samples with higher O:Li ratios, up to 0.8, showed additional mixed aggregates present. All solutions containing mixed aggregates were also shown to contain hydrocarbon soluble lithium hydride. A study of lithium 2-ethyl-1- hexoxide indicated that it aggregates in solution as well.

Polymer hydrogel films change their properties in response to environmental change. This remarkable phenomenon results in many potential applications of polymer hydrogel films. In this thesis colored thermo-sensitive poly(N-isopropylacrylamide) (PNIPAAm) hydrogel film was prepared by firstly synthesizing polymer latex and secondarily crosslinking the nanoparticles and casting the polymers onto glass. The shape-memory effect has been observed when changing the environmental temperature. The temperature-dependent of turbidity of polymer hydrogel film was measured by HP UVVisible spectrophotometer. This intelligent hydrogel might be used in chemomechanical systems and separation devices as well as sensors. Polymer adsorption plays an important role in many products and processes. In this thesis, surfactant-free three-dimensional polystyrene (PS) nanoparticle network has been prepared. The infrared spectroscopy and solubility experiment are performed to prove the crosslinking mechanism, also the BET method was used to measure the adsorption and desorption of polystyrene network. The BET constant (C) is calculated (C=6.32). The chemically bonded polymer nanoparticle network might have potential applications as catalyst or used for chromatographic columns.

A variable temperature 1H, 13C, and 6Li NMR study of n-propyl-6Li-lithium showed five different aggregates, similar to that in the literature as (RLi)n, n= 6, 8, 9, 9, 9. There were also a number of additional new species, identified as lithium hydride containing aggregates. Unexpectedly, a series of 13C{1H} 1-D NMR experiments with selective 6Li decoupling showed evidence for 13C-6Li spin-spin coupling between the previously reported (RLi)n aggregates and various hydride species.

The preparation of layered double hydroxides via co-precipitation of a divalent/trivalent metal solution against a base results in 1 mm LDH particles with a disorganized metal lattice. Research was performed to address these morphological issues using techniques such as Ostwald ripening and precipitation via aluminate. Another interesting issue in layered double hydroxide materials is the uptake and orientation of anions into the interlayer. Questions about iron cyanide interlayer anions have been posed. Fourier transform infared spectroscopy and powder x-ray diffraction have been used to investigate these topics. It was found that factors such as orientation, anion charge, and anion structure depended on the divalent/trivalent metal ratio of the hydroxide layer and reactivity time. The cyanide self-addition reaction is an important reaction of classical prebiotic chemistry. This reaction has been shown to give rise to amino acids, purines and pyrimidines. At cyanide concentrations similar to that expected on the early earth, hydrolysis to formamide rather than self-addition occurs. One theory to alleviate this side reaction is the use of minerals or clays that are thought to concentrate and catalyze prebiotics of interest. Layered double hydroxides have been studied as a catalyst for this reaction.

The thermochemistry of several species, and the kinetics of various H atom radical reactions relevant to atmospheric and combustion chemistry were investigated using ab initio theoretical techniques and the flash photolysis / resonance fluorescence technique. Using ab initio quantum mechanical calculations up to the G3 level of theory, the C-H bond strengths of several alkanes were calculated. The bond strengths were calculated using two working reactions. From the results, it is apparent that the bond strengths decrease as methyl groups are added to the central carbon. The results are in good agreement with recent experimental halogenation kinetic studies. Hydrogen bond strengths with sulfur and oxygen were studied via CCSD(T) theory, together with extrapolation to the complete basis set limit. The results for the bond dissociation energies (ground state at 0 K, units: kJ mol-1) are: S-H = 349.9, S-D = 354.7, HS-H = 376.2, DS-D = 383.4, and HO-H = 492.6. These data compare well with experimental literature. The rate constants for the isotopic reactions of H + H2S, D + H2S, H + D2S, and D + D2S are studied at the QCISD(T)/6-311+G(3df,2p) level of theory. The contributions of the exchange reaction versus abstraction are examined through transition state …

The reaction between o-phenylenediamine and 2,3-dichloromaleic anhydride has been probed and found to give 2,3-dichloropyrrolo[1,2-a]- benzimidazol-1-one as the major product. Chlorine substitution in 2,3-dichloropyrrolo[1,2-a]benzimidazol-1-one by added benzylthiol occurs in the presence of pyridine to provide the corresponding monosulfide and disulfide derivatives. The first benzylthiol ligand undergoes reaction at the C-3 position of the five-membered pyrrolo-1-one ring, with the addition of the second benzylthiol ligand occurring at the remaining chlorine-substituted carbon. The mono- and disulfide derivatives have been isolated and characterized in solution by NMR, IR, and UV-vis spectroscopies, and the solid-state structure of 2,3-di(benzylthio)pyrrolo[1,2-a]benzimidazol-1-one has been established by X-ray crystallography.

The kinetics of the pressure dependent O + SO2 + Ar reaction have been investigated using laser photolysis resonance fluorescence at temperatures of 289 K, 399 K, 581 K, 699 K, 842 K and 1040 K and at pressures from 30-665 torr. Falloff was observed for the first time in the pressure dependence. Application of Lindemann theory yielded an Arrhenius expression of k(T) = 3.3 x 10-32exp(-992/T) cm6 molecule-1 s-1 for the low pressure limit and k(T) = 8.47 x 10-14exp(-468/T) cm3 molecule-1 s-1 for the high pressure limit at temperatures between 289 and 842 K. The reaction is unusual as it possesses a positive activation energy at low temperature, yet at higher temperatures the activation energy is negative, illustrating a reaction barrier.

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 …

Computational techniques were employed to investigate pathways that would improve the properties and characteristics of transition metal (i.e., ruthenium) catalysts, and to explore their mechanisms. The studied catalytic pathways are particularly relevant to catalytic hydroarylation of olefins. These processes involved the +2 to +3 oxidation of ruthenium and its effect on ruthenium-carbon bond strengths, carbon-hydrogen bond activation by 1,2-addition/reductive elimination pathways appropriate to catalytic hydrogen/deuterium exchange, and the possible intermediacy of highly coordinatively unsaturated (e.g., 14-electron) ruthenium complexes in catalysis. The calculations indicate a significant decrease in the Ru-CH3 homolytic bond dissociation enthalpy for the oxidation of TpRu(CO)(NCMe)(Me) to its RuIII cation through both reactant destabilization and product stabilization. This oxidation can thus lead to the olefin polymerization observed by Gunnoe and coworkers, since weak RuIII-C bonds would afford quick access to alkyl radical species. Calculations support the experimental proposal of a mechanism for catalytic hydrogen/deuterium exchange by a RuII-OH catalyst. Furthermore, calculational investigations reveal a probable pathway for the activation of C-H bonds that involves phosphine loss, 1,2-addition to the Ru-OH bond and then reversal of these steps with deuterium to incorporate it into the substrate. The presented results offer the indication for the net addition of aromatic C-H …

This study is based on survey responses of 224 general chemistry instructors at United States (U.S.) community colleges and universities representing 46 states. The mean values of General Chemistry Topic Coverage (GCTC) score, developed by this researcher specifically for this dissertation study as a measure of course content, were statistically analyzed. The aim of this study is to answer five research questions: (a) Is there a difference in mean GCTC scores between U.S. community colleges and four-year colleges and universities? (b) If there is a difference in mean GCTC score between the two study groups, what are the observed differences in subtopics covered between community colleges and four-year colleges and universities? (c) Considering both community colleges and universities, is there a difference in mean GCTC score between the different designated U.S. regions? (d) Considering both community college and university professors, is there a difference in GCTC score for professors with a master's degree compared to those with a doctorate?, and (e) Is there a correlation between GCTC score and the percentage of students that major in science? Results indicate that there is a statistically significant difference in course content between community colleges and universities, there is a statistically significant difference …

The tetraruthenium cluster H4Ru4(CO)12 has been studied for its reactivity with the unsaturated diphosphine ligands (Z)-Ph2PCH=CHPPh2, 4,5-bis (diphenylphosphino)-4-cyclopenten-1,3-dione, bis(diphenyphosphino)benzene and 1,8- bis(diphenyl phosphino)naphthalene under thermal, near-UV photolysis, and Me3NO-assisted activation. All three cluster activation methods promote loss of CO and furnish the anticipated substitution products that possess a chelating diphosphine ligand. Clusters 1, 2, 3 and 4 have been characterized in solution by IR and NMR spectroscopies, and these data are discussed with respect to the crystallographically determined structures for all new cluster compounds. The 31P NMR spectral data and the solid-state structures confirm the presence of a chelating diphosphine ligand in all four new clusters. Sealed NMR tubes containing clusters 1, 2, 3 and 4 were found to be exceeding stable towards near-UV light and temperatures up to ca. 100°C. The surprisingly robust behavior of the new clusters is contrasted with the related cluster Ru3(CO)10(bpcd) that undergoes fragmentation to the donor-acceptor compound Ru2(CO)6(bpcd) and the phosphido-bridged compound Ru2(CO)6 (µ-PPh2)[µ-C=C(PPh2)C(O)CH2C(O)] under mild conditions. The electrochemical properties have been investigated in the case of clusters 1 and 2 by cyclic voltammetry, and the findings are discussed with respect to the reported electrochemical data on the parent cluster H4Ru4(CO)12.

Flat dendrimers, consisting of a hexavalent aromatic core and rigid ethynyl units locked in place by ether connections were developed based upon the divergent synthetic method. Alternating functional groups were adopted on each site of the hexa-substituted benzene, in order to avoid undesired cyclization pathways. The flat structures of conjugated dendrimers would allow investigation on the discotic liquid crystal properties. In addition, these ethylnyl dendrimers are expected to show directed energy and electron transfer with a highly conjugated system, and thus are effective in the preparation of photoreactive materials such as electronic sensors or light harvesting materials. Conjugated polycyclic aromatic hydrocarbons, consisting of naphthalene, anthracene, pyrene, and phenanthrene groups connected via 1,3,5-triethynylbenzene cores, were synthesized. These molecules exhibited luminescence properties and the π-complexation with a mercury trifunctional lewis acid are expected to enhance the phosphorescence in the presence of the heavy metal due to the spin-orbit coupling. Besides, owing to the presence of heavy metal atom in the Au (I) complexes linked by s-bonded triethynyltriphenylene luminophore, the phosphorescence occurs from a metal-centered emission. The conjugated organic luminophores have been developed to produce excellent quantum efficiencies, brightness, and long lifetimes.

The novel instrumentation of nanomanipulation coupled to nanospray mass spectrometry and its applications are presented. The nanomanipulator has the resolution of 10nm step sizes allowing for specific fine movement used to probe and characterize objects of interest. Nanospray mass spectrometry only needs a minimum sample volume of 300nl and a minimum sample size of 300attograms to analyze an analyte making it the ideal instrument to couple to nanomanipulation. The nanomanipulator is mounted to an inverted microscope and consists of 4 nano-positioners; these nano-positioners hold end-effectors and other tools used for manipulation. This original coupling has been used to enhance the current abilities of cellular probing and trace fiber analysis. Experiments have been performed to demonstrate the functionality of this instrument and its capabilities. Histidine and caffeine have been sampled directly from single fibers and analyzed. Lipid bodies from cotton seeds have been sampled indirectly and analyzed. The few applications demonstrated are only the beginning of nanomanipulation coupled to nanospray mass spectrometry and the possible applications are numerous especially with the ability to design and fabricate new end-effectors with unique abilities. Future study will be done to further the applications in direct cellular probing including toxicology studies and organelle analysis of …

Aluminum was deposited onto both Teflon AF and Parylene AF surfaces by chemical vapor deposition of trimethylaluminum. This work shows that similar thin film (100 Angstroms) aluminum oxide adlayers form on both polymers at the low temperature dosing conditions used in the studies. Upon anneal to room temperature and above, defluorination of the polymer surfaces increased and resulted in fluorinated aluminum oxide adlayers; the adlayers were thermally stable to the highest temperatures tested (600 K). Angle-resolved spectra showed higher levels of fluorination toward the polymer/adlayer interface region. Copper films were also deposited at low temperature onto Teflon AF using a copper hexafluoroacetylacetonate-cyclooctadiene precursor. Annealing up to 600 K resulted in the loss of precursor ligands and a shift to metallic copper. As with aluminum adlayers, some polymer defluorination and resulting metal (copper) fluoride was detected. Parylene AF and polystyrene films surfaces were modified by directly dosing with water vapor passed across a hot tungsten filament. Oxygen incorporation into polystyrene occurred exclusively at aromatic carbon sites, whereas oxygen incorporation into parylene occurred in both aromatic and aliphatic sites. Oxygen x-ray photoelectron spectra of the modified polymers were comparable, indicating that similar reactions occurred. The surface oxygenation of parylene allowed enhanced reactivity …

Substitution of the 1,5-cyclooctadiene (cod) ligand in PtCl2(cod) (1) by the diphosphine ligand 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd) yields PtCl2(bpcd) (2). Knoevenagel condensation of 2 with 9-anthracenecarboxaldehyde leads to the functionalization of the bpcd ligand and formation of the corresponding 2-(9-anthracenylidene)-4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (abpcd) substituted compound PtCl2(abpcd) (3), which is also obtained from the direct reaction of 1 with the abpcd ligand in near quantitative yield. The reaction of 3 with disodium maleonitriledithiolate (Na2mnt) affords the chelating dithiolate compound Pt(mnt)(abpcd) (4). The reaction of PtCl2(bpcd) (2) with 4-methyl-1,2-benzene dithiol under basic conditions affords Pt(tdt)(bpcd) (5). Compounds 2-5 have been fully characterized in solution by IR and NMR spectroscopies (1H and 31P), and their molecular structures established by X-ray crystallography. The electrochemical properties of 2&#8209;5 have examined by cyclic voltammetry, and the nature of the HOMO and LUMO levels in systems 2-4 has been established by MO calculations at the extended Hückel level, the results of which are discussed with respect to electrochemical data and related diphosphine derivatives. In addition the new compounds 2-5 have been isolated by column chromatography and characterized by IR, UV-Vis spectroscopy.

The major topics discussed are all relevant to the bright phosphorescent emissions of coinage metal complexes (Cu(I), Ag(I) and Au(I)) with an explanation of the theoretical background, computational results and ongoing work on the application in materials and optoelectronic devices. Density functional computations have been performed on the majority of the discussed complexes and determined that the most significant distortion that occurs in Au(I)-phosphine complexes is a near and beyond a T-shape within the P-Au-P angle when the complexes are photoexcited to the lowest phosphorescent excited state. The large distortion is experimentally qualified with the large Stokes' shift that occurs between the excitation and emission spectra and can be as large as 18 000 cm-1 for the neutral Au(I) complexes. The excited state distortion has been thoroughly investigated and it is determined that not only is it pertinent to the efficient luminescence but also for the tunability in the emission. The factors that affect tunability have been determined to be electronics, sterics, rigidity of solution and temperature. The luminescent shifts determined from varying these parameters have been described systematically and have revealed emission colors that span the entire visible spectrum. These astounding features that have been discovered within studies of …

The optimal conditions for deposition of zinc-nickel alloys onto stainless steel discs in alkaline solutions have been examined. In the past cadmium has been used because it shows good corrosion protection, but other methods are being examined due to the high toxicity and environmental threats posed by its use. Zinc has been found to provide good corrosion resistance, but the corrosion resistance is greatly increased when alloyed with nickel. The concentration of nickel in the deposit has long been a debated issue, but for basic solutions a nickel concentration of 8-15% appears optimal. However, deposition of zinc-nickel alloys from acidic solutions has average nickel concentrations of 12-15%. Alkaline conditions give a more uniform deposition layer, or better metal distribution, thereby a better corrosion resistance. Although TEA (triethanolamine) is most commonly used to complex the metals in solution, in this work I examined TEA along with other complexing agents. Although alkaline solutions have been examined, most research has been done in pH &#8805; 12 solutions. However, there has been some work performed in the pH 9.3-9.5 range. This work examines different ligands in a pH 9.3-9.4 range. Direct potential plating and pulse potential plating methods are examined for optimal platings. The …