The semiconductor industry is continually challenged to maintain the trend identified in 1965 by Gordon Moore of increasing the density of transistors on an integrated circuit. These advances have been achieved by increasing the resolution that can be printed with photolithography, traditionally by decreasing the exposure wavelength. Decreasing the exposure wavelength from 193 nm, the current state of the art, presents significant technical challenges. To circumvent these challenges, resolution can be increased by enabling increases in numerical aperture (without changing the exposure wavelength), using immersion lithography. In immersion lithography, the air gap between the photoresist-coated wafer and lens is replaced with a high refractive index fluid. Immersion lithography has been demonstrated with water as the immersion fluid. With water immersion lithography at 193 nm, the maximum resolution that can be printed can be decreased from 65 nm to 45 nm. To enable further resolution increases, immersion fluids with a higher index than water are needed. The requirements for next generation high index fluids are: an index of refraction higher than water, high transparency, and physical properties similar to water. A variety of methods to identify a high index fluid were completed. First, the optical properties of aqueous solutions of metal cations with varying anions were tested. A series of linear, cyclic, and polycyclic alkanes were also studied, since saturated systems have electronic transitions at wavelengths less than 200 nm, to provide the necessary transparency at 193 nm. Large alkane groups were also incorporated into either the cation or anion of a salt to develop an aqueous solution with the optical properties of a saturated hydrocarbon. In addition to these empirical surveys, a modeling approach was used to develop “designer” absorbance spectra that would correspond to fluids with a high index and low absorbance at 193 nm. Additionally, in Appendix D, the results of an electrochemical study of the diffusion coefficient of ferrocene methanol in poly(ethylene glycol) diacrylate hydrogels of varying molecular weight and water content will be presented. The results of these mass transport studies can be used to qualitatively understand the mass transport characteristics of additional species in the hydrogel. / text

No description available.

Paraffin activation has practical implications in the replacement of current petrochemical feedstocks (olefins), by utilizing economical and easily accessible alkanes, which may result in more efficient strategies for fine chemical synthesis and the proficient use of energy. However, the chemical inertness of paraffins limits their conversion to more valuable products. Several pincer chelate complexes are utilized in stoichiometric and catalytic C–H activation. These pincer ligands have attained much interest in that they are part of a system, which displays high stability, activity and variability. In this study four aminodiphosphine (PNP) pincer ligands were successfully synthesized and characterized by NMR, IR and HRMS. To investigate the steric effects on the metal center, four different functional groups on the nitrogen atom were used, a cyclic ring (cyclohexyl (3.1)) branched chain (iso-propyl (3.2)); straight chain (pentyl (3.3)); and aromatic ring (benzyl (3.4)). The ligands were successfully complexed to the transition metals iridium and cobalt and characterized by elemental analyses, IR, HRMS and thermogravimetric measurements. The thermal behaviour of the ligands showed that ligands 3.1-3.3 displayed similar decomposition patterns. Similar fragmentation patterns were observed for the iridium and cobalt complexes containing ligands 3.1 and 3.3. The complexes were tested in the oxidation of n-octane in two solvent systems, DCM and MeCN with H2O2 and t-BuOOH as the oxidants. The optimum substrate to oxidant ratio was found to be 1:5. No conversion was observed with H2O2. The conversion in DCM for the iridium catalysts was much higher than that of the cobalt catalyst. However, higher conversion was obtained in MeCN for the cobalt catalysts. No conversion was observed for the iridium catalyst in MeCN. The selectivity to ketones was much higher than to the alcohols, with only the C(1) position being most selective to the alcohols. The in situ, single pot testing of n-octane using a ruthenium precursor and ligand 3.1- 3.4 undertaken in DCM showed no conversion, whilst in MeCN a conversion of 17% was observed. The selectivity was similar to that obtained by the cobalt catalysts in MeCN. All testing showed that the catalyst containing ligand 3.1 was the most active giving the highest conversions in different solvent systems, which is attributed to the bite angle effect. / Thesis (M. Sc.)-University of KwaZulu-Natal, Durban, 2011.

Base-promoted CHA of unstrained alkanes with 5,10,15,20-tetratolylporphyrinatorhodium complexes, Rh(ttp)X (X = Cl, H, Rh(ttp)), has been achieved. Rh(ttp)Cl, reacted with n-pentane, n-hexane, n-heptane, c-pentane and c-hexane in the presence of potassium carbonate at 120 °C in 6 to 24 h to give rhodium porphyrin alkyls, Rh(ttp)R, in 29--76% yields. Mechanistic investigations suggested that Rh 2(ttp)2 and Rh(ttp)H are key intermediates for the parallel CHA step. The roles of base are (i) to facilitate the formation of Rh(ttp)Y (Y- = OH-, KCO3 -), (ii) to enhance the CHA rate with alkane and generate Rh(ttp)H by a Rh(ttp)Y species which is more reactive than Rh(ttp)Cl, and (iii) to provide a parallel CHA pathway by Rh2(ttp)2. / c-Octane reacted with Rh(ttp)Cl at 120 °C in 7.5 h in the presence of K2CO3 to yield Rh(ttp)( n-octyl) and Rh(ttp)H in 33% and 58% yields, respectively. Mechanistic investigations indicate that the CCA product is generated from the Rh II(ttp)-catalyzed 1,2-addition of c-octane with Rh(ttp)H. Reaction of c-octane and Rh(ttp)H/Rh2(ttp) 2 (10:1) selectively yielded Rh(ttp)(n-octyl) in 73% at 120 °C in 15 h. The catalyst RhII(ttp) radical cleaves the C-C bond of c-octane to form to a Rh(ttp)-alkyl radical, which then abstracts a hydrogen atom from Rh(ttp)H to generate the Rh(ttp)( n-octyl), and subsequently leading to regeneration of the Rh II(ttp) radical. (Abstract shortened by UMI.) / K2CO3-promoted CHA of the ring-strained cycloheptane with Rh(ttp)Cl at 120 °C in 6 h gave the CHA product Rh(ttp)( c-heptyl) and together with, unexpectedly, the CCA product Rh(ttp)Bn, in 30% and 24% yields, respectively. Mechanistic studies revealed that Rh(ttp)( c-heptyl) undergoes beta-hydride elimination in neutral condition or beta-proton elimination in basic condition followed by reprotonation to give rhodium(III) porphyrin hydride, Rh(ttp)H, and c-heptene. Successive base-promoted CHA of c-heptene with Rh(ttp)H, followed by beta-proton elimination, generates cycloheptatriene. The CHA of cycloheptatriene with Rh(ttp)H formed Rh(ttp)(c-heptatrienyl), which underwent rearrangement with carbon-carbon cleavage at 120 °C in 16 d to yield Rh(ttp)Bn in 96% yield. / The objectives of this research focus on the investigation of carbon-hydrogen bond activation (CHA) and carbon-carbon bond activation (CCA) of alkanes by rhodium porphyrin complexes as well as the mechanistic understanding. / Chan, Yun Wai. / Adviser: Kin Shing Chan. / Source: Dissertation Abstracts International, Volume: 73-02, Section: B, page: . / Thesis (Ph.D.)--Chinese University of Hong Kong, 2010. / Includes bibliographical references. / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Electronic reproduction. [Ann Arbor, MI] : ProQuest Information and Learning, [201-] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstract also in Chinese.

Reaction of phenyl vinyl sulfoxide with the lithium enolates of simple ketones of varying ring size (cyclopentanone, cycloheptanone and cyclooctanone) under controlled cyclisation conditions followed by subsequent oxidation resulted in the formation of the bicyclo[n.2.0]alkan-1-ols 253-255, 262, 263, 265, 268 and 269 in conjunction with alkylated species 256, 257, 264, 266 and 267. The ratio of bicyclo[n.2.0]alkan-1-ols to alkylated ketone formation observed was dependent on a number of factors including the variation of enolate reactivity between the different ring sizes, conversion of phenyl vinyl sulfoxide, time, temperature and concentration of reaction and the stability and steric strain observed in the final bicyclo[n.2.0]alkan-1-ol product. X-ray crystal structures of 253, 262 and 265 were obtained and a structural study showed that as the overall steric strain in the bicyclo[n.2.0]alkan-1-ol product is decreased there is a corresponding increase in product distribution in favour of bicyclo[n.2.0]alkan-1-ol formation in conjunction with increased yields. Selected substituted and functionalised ketones (2-methylcyclopentanone, 2,6-dimethylcyclohexanone, 2-methylcyclohexanone and 1,4-cyclohexanedione mono-ethylene ketal) also reacted in the cyclisation reaction to give bicyclo[n.2.0]alkan-1-ols 270, 271, 277, 278, 281, 282, 285 and 286 in conjunction with alkylated products 272, 279, 280, 283, 284 and 287. Incorporation of substitution at the bridgehead and C2 position had a role in the preference of the major stereochemical isomer observed for a bicyclo[n.2.0]alkan-1-ol (n = 3, 4). A structural comparison of the X-ray crystal structures of 278, 281 and 286 indicated that the pseudo chair conformation of the six-membered ring influenced ring torsion and bond angles in the bicyclo[4.2.0]octanol ring system. Two model studies were selected to illustrate the potential application of the cyclisation process as methodology towards natural product synthesis or complex ring systems. No bicyclo[n.2.0]alkan-1-ol formation was evident in an intramolecular example using the starting ketone 291 in which the electrophile is tethered to the ketone. 2,6-Dimethyl-2-cyclohexen-1-one 301 considered as a model study towards the synthesis of the antibiotic mellolide, upon reaction with phenyl vinyl sulfoxide and oxidation displayed poor reactivity. The novel bicyclo[2.2.2]octanones 303, 304 and 305 were formed in very low yields. The lack of reactivity of the ketones 2,6-dimethyl-2-cyclohexen-1-one, 1,2-cyclohexanedione and 1,4-cyclohexanedione towards bicyclo[n.2.0]alkan-1-ol formation suggested that conjugation in the enolate prior to reaction with phenyl vinyl sulfoxide was not favourable. The non-reactivity of these ketones and the hindered ketone camphor indicated the potential limitations to the cyclisation methodology. However, conversion of the ketal functionality of 286 to a ketone resulted in the formation of the functionalised bicyclo[4.2.0]octanol 288 providing positive indications for further synthetic applications.

Thesis (Ph. D.)--University of Washington, 2000. / Vita. Includes bibliographical references (leaves 148-156).

Not available / text

Using the new Picker flow calorimeter, the excess heat capacity (C(,p)('E)) has been measured for systems containing normal, branched and cyclic alkanes. The results indicate two unusual effects: (1) a large negative contribution due to the destruction of orientational order in a pure n-alkane component, and (2) a positive contribution attributed to the "condensation" of a more freely-moving molecule or segment on a sterically-hindered branched alkane, resulting in a restriction of rotational movement, i.e. creation of order in the solution. Mixtures of cycloalkanes and their methyl derivatives also show unexpected positive effects in the excess heat capacity. Thus the plate-like cyclopentane molecule gives positive C(,p)('E) values when mixed with other plate-like methyl derivatives of cyclohexane suggesting a hindering of its molecular rotation. / Cyclohexane mixed with globular branched and cyclic alkanes shows S-shaped C(,p)('E) curves, negative at low concentration of cyclohexane but positive at high, indicating the possibility of a restriction of cyclohexane motion. / Effects of order are also apparent in the equation of state of a liquid. The thermal pressure coefficient for systems containing n-hexadecane has been found to be anomalous and is explained by a lowering of the internal energy of n-hexadecane by orientational order. / Excess volume (V('E)) has been studied for systems of branched and normal alkanes by investigating different effects contributing to the total V('E), particularly an important effect of a difference in thermal pressure coefficients of the two components.

Thesis (Ph. D.)--University of Missouri-Columbia, 2007. / The entire dissertation/thesis text is included in the research.pdf file; the official abstract appears in the short.pdf file (which also appears in the research.pdf); a non-technical general description, or public abstract, appears in the public.pdf file. Title from title screen of research.pdf file (viewed on March 11, 2008) Includes bibliographical references.

Thesis (Ph. D.)--University of Washington, 2007. / Vita. Includes bibliographical references (leaves 119-130).