This study was intended to provide a fuller understanding of the surface chemical processes which result in the corrosion of ferrous materials.

The tricobalt cluster PhCCo3(CO)9 (1) reacts with the bidentate phosphine ligand 2,3-bis(diphenylphosphino)maleic anhydride (bma) in the presence of added Me3NO to give the diphosphine-substituted cluster PhCCo3(CO)7(bma) (2). Cluster 2 is unstable in solution, readily losing CO to afford Co3(CO)6[(μ2-η2/η1-C(Ph)C=C(PPh2)C(O)OC(O)](μ2-PPh2) (3) as the sole observed product. VT-31P NMR measurements on cluster 2 indicate that the bma ligand functions as both a chelating and a bridging ligand. At -97 °C, 31P NMR analysis of 2 reveals a Keq of 5.7 in favor of the bridging isomer. The bridged bma cluster 2 is the only observed species above -50°C. The solid-state structure of 2 does not correspond to the major bridging isomer observed in solution but rather the minor chelating isomer. The conversion of 2 to 3 followed first-order kinetics, with the reaction rates being independent of the nature of the reaction solvent and strongly suppressed by added CO, supporting a dissociative loss of CO as the rate-determining step. The activation parameters for CO loss were determined to be ΔH≠ = 29.9 ± 2.2 kcal/mol and ΔS≠ = 21.6 ± 6 eu.

The tricobalt cluster PhCCo₃(CO)₉ (1) reacts with the bidentate phosphine ligand 2,3-bis(diphenylphosphino)maleic thioanhydride (bta) with added Me₃NO to yield PhCCo₃(CO)₇(bta) (2), which upon heating overnight yields Co₃(CO)₆(μ₂-η²,η¹-C(Ph)C=C(PPH₂)C(O)SC(O)) (μ₂-PPh₂) (3). Cluster (3) has been isolated and characterized by FT-IR and ³¹P NMR spectroscopy. Structural determination of the cluster has been demonstrated by X-ray diffraction analysis. Cluster (3) is analogous to the cluster synthesized by Richmond and coworkers. The redox properties of (3) have been examined by cyclic voltammetry and the data are reported within.

Chapter I describes the synthesis of a trishomocubyl helical tubuland diol and some aspects of its inclusion chemistry. Thus, all three isomers of 4,7-dimethylpentacyclo[6.3.0.0^2,6.0^3,10.0^5,9]undecane-4,7-diol have been prepared and their X-ray structures have been determined. The syn,syn-isomer crystallizes in a double-stranded hydrogen-bonded lattice, while anti,syn-isomer forms a hydrogen-bonded layer lattice. In contrast, the anti,anti-isomer is a new member of the helical tubuland diol host family; its crystal lattice consists of parallel canals with a trefoil-shaped cross-section of area 25.4 Å^2. Chapter II describes the synthesis of new molecular clefts. These molecular clefts have been synthesized via base-promoted reactions of 3,6-diaryl-l,2,4,5-tetrazines with tetracyclo[6.3.0.0^4,11.0^5,9]undecane-3,6-dione and with tricyclo[6.3.0.0^2,6]undecane-3,11-dione, respectively. Compounds of this type are of interest as a potential new class of host molecules for use in host-guest complexation studies. Chapter III reports the synthesis of stereospecifically deuterated spiro(oxetane-3,8'-pentacyclo[5.4.0.0^2,6.0^3,10.0^5,9]undecanes) and their acid-promoted ring opening and concomitant rearrangements. The deuterium-containing reaction products have been characterized via analysis of their NMR and mass spectra. The results strongly suggest that intramolecular 1,5-hydride shifts provide an important pathway through which the acid promoted rearrangements occur. Chapter IV reports the oxidation of heptacyclo-[6.6.0.0^2,6.0^3,13.0^4,11.0^5,9.0^10,14] tetradecane (HCTD) via application of Barton's "GoAgg" systems. The products have been characterized by NMR and …

Tensile properties, namely the elastic modulus, tensile strength, percent of elongation at yield and at the break were determined for the pure components and blends. The results are connected to the respective phase diagrams and demonstrate that blending makes property manipulation possible. Blends for which the mechanical properties are better than those of pure EPs can be obtained.

Spectrofluorometric probe methods are developed and examined regarding their ability to model preferential solvation around probe molecules in binary solvents. The first method assumes that each fluorophore is solvated by only one type of solvent molecule and that each fluorophore contributes to the emission intensity. Expressions for this model are illustrated using fluorescence behavior of pyrene, benzo[e]pyrene, benzo[ghi]perylene, and coronene dissolved in binary n-heptane + 1,4-dioxane and n-heptane + tetrahydrofuran mixtures. The second method treats the solvational sphere as a binary solvent microsphere, with the fluorophore's energy in both the ground and the excited states mathematically expressed using the "nearly ideal binary solvent" (NIBS) model. Expressions derived from this model are illustrated using fluorescence behavior of 9,9'-bianthracene and 9,9*-bianthracene-10-carboxaldehyde in binary toluene + acetonitrile and dibutyl ether + acetonitrile.

Palladium catalyzed reactions of derivatives of 2,4-diiodophenol are explored. Coupling reactions with a series of terminal alkynes and formylation are found to be efficient and regioselective. Coupling with stananne reagents and alkenes do not work. The nature of the oxygen protecting group is critical. The phytotoxic natural product, Eutypine, is synthesized by using regioselective formylation and alkyne coupling. An approach to the plant antimicrobial compound Plicatin B is examined.

The fluorescence spectrum of many polycyclic aromatic compounds (PACs) depends upon solvent polarity. The emission spectrum of PAC monomers consists of several major vibronic bands labeled I, II, etc., in progressive order. Emission intensity enhancement of select bands is observed in polar solvents.

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.

This research was designed to investigate the hydration reaction of fly ash when exposed to water. The effects that calcium nitrate and calcium formate have on the hydration reactions were also examined.