Thesis (Ph. D.)--Ohio State University, 2005. / Title from first page of PDF file. Document formatted into pages; contains xiv, 172 p.; also includes graphics (some col.). Includes bibliographical references (p. 167-172). Available online via OhioLINK's ETD Center

Thesis (Ph.D.)--Boston University / The heat capacity (Cp) of four Beta-quinol clathrates of carbon monoxide with y = 0.460, 0.626, 0.752 and 0.810, and of one HBr clathrate with y = 0.811 have been measured from 15 to 300K. Cp for 3C6H4(OH)2 * yCO is found to be a linear function of y. The partial molal heat capacity and entropy of clathrated CO and hte heat capacity and entropy of 3 moles of Beta-quinol have been calculated. The respective values at 298.15K are: Cco = 9.76 +/- 0.8 cal. deg.^-1mol^-1; SCO = 20.94 +/- 0.20 cal. deg.^-1mole^-1; Cp^Q = 98.72 cal. deg.^-1; S^Q = 100.28 cal. deg.^-1. [TRUNCATED]

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When syn-benzaldoxime was reacted with carbon monoxide containing about 0.04 volume percent of hydrogen and dicobalt octacarbonyl in benzene solution at elevated temperatures and pressures the following compounds were produced; sym-dibenzylurea (35%), monobenzylurea (10%) and benzaldehyde (10%). Also isolated were 15% yields of two unidentified components referred to as compounds A and B. When benzophenone oxime was subjected to the same reaction conditions the major product was 3-phenylphthalimidine (75%). Also isolated was a 5% yield of an unidentified component called compound B. It was demonstrated that under the reaction conditions used considerable amounts of dicobalt octacarbonyl are needed for successful reaction. When the octacarbonyl was present in only catalytic amounts the course of the observed reaction was greatly affected and the major isolated product was benzophenone (70%). Small amounts of 3-phenylphthalimidine and of the original oxime were also isolated. When the 0-methyl ether of benzophenone oxime was reacted the only product isolated was 3-phenylphthalimidine in 75% yield. Reaction pressures corrected to constant temperature are plotted against reaction time for each substrate and the results discussed. A new method of synthesizing the 0-methyl ether of benzophenone oxime (using 0-methyl hydroxylamine), and a dichromate-acetic acid oxidation of sym-dibenzylurea giving a high yield of dibenzoylurea are described. A platinum oxide in acetic acid reduction of 3-phenylphthalimidine which reduced both benzene rings but left the lactam group intact is also described. Infrared spectra are included for all compounds obtained. / Science, Faculty of / Chemistry, Department of / Graduate

An instrument is described which is capable of measuring the action spectrum of the removal of CO inhibition of respiration by light. In the method employed here, a cell suspension in a CO-O₂ atmosphere is alternately exposed to two wavelengths of light. Their photochemical effects are balanced using an 0₂ electrode as the null detector. The light intensities at the balance points from a series of wavelength pairs are used to determine the ratios of the extinction coefficients of the CO - oxidase complex, at the various wavelengths, to the extinction coefficient at a standard wavelength. An action spectrum for Bakers yeast is shown. / Science, Faculty of / Physics and Astronomy, Department of / Graduate

The binding energies and momentum profiles for each of the valence orbitals of CO and H₂S have been measured by high momentum resolution electron momentum spectroscopy. The experimental momentum profiles are compared on a quantitative basis within the Target Hartree-Fock Approximation to theoretical calculations using SCF wavefunctions ranging in quality from minimal basis to Hartree-Fock limit. Calculated momentum distributions for the 5σ orbital of CO are shown to be very basis set dependant while calculated momentum distributions of the CO 3σ, 4σ and 1π orbitals change very little with improvements in the wavefunction beyond the double-zeta level. The CO 1π orbital is not very well described in the low momentum region even at the Hartree-Fock limit with basis set saturation including diffuse functions. While the 4a₁, and 2b₂ momentum profiles of H₂S are well described using even minimal basis calculations, diffuse functions must be included in the basis set to describe the 2b₁, and 5a₁, momentum profiles. The experimental momentum profiles of H₂S are also compared with full ion-neutral overlap calculations incorporating correlation in the ground state and correlation and relaxation in the final ion state. These calculations are very similar to the Hartree-Fock level momentum distributions, indicating that correlation is not very important in describing the momentum profiles of H₂S. The binding energy spectra and momentum profiles of the inner valence region of both CO and H₂S are studied in detail. Peaks in the CO binding energy spectrum at 24.1 and 28.3 eV are assigned as satellites 4σ and 1π main lines respectively while the structure above 30 eV is shown to be predominantly due to satellites of the 3σ orbital. The intense structure in the inner valence region of H₂S is found to arise predominantly from the 4a₁, orbital. The assignments of the inner valence spectra of both molecules is confirmed within experimental uncertainties by the spectroscopic sum rule. / Science, Faculty of / Chemistry, Department of / Graduate

Kinetic studies are described for the activation of carbon monoxide, molecular hydrogen, and molecular oxygen by rhodium halide complexes in solution. Carbon monoxide reacts with bromorhodate(III) and bromocarbon-ylrhodate(III) complexes to produce the anionic species, [Rh(C0)2Br2]⁻. The reaction of [RhBr4(H2O)2]²⁻ in acid bromide solutions involves initial formation of a RhIII(C0) substitution product, which then undergoes reductive carbonylation: [Eqn 1 and 2] Further production of RhI is autocatalytic due to a more effective reduction via a CO independent path that involves a [RhIII…Br…RhI(CO)2I] bridged intermediate. Reductive carbonylation of the pentabromocarbonyl-rhodate(III) complex in aqueous HBr solution proceeds in a similar manner. Decomposition of RhIIICO) by water to produce Rh1 species (equations 1 and 2) results in the autocatalytic formation of [Rh(C0)2Br2]⁻ through a step that again involves a bromide-bridged intermediate, [(CO)RhIII…Br ---RhI(C0)2] . Carbon monoxide can be catalytically activated by rhodium(III) for the reduction of substrates such as ferric ion. Kinetic studies sug-gest a mechanism involving reduction of [Rh(C0)Br5]²⁻ by water. Data are consistent with the following scheme: [Eqn 3] Acid solutions of RhBr3•2H20 activate H2 for the reduction of FeIII . Formation of a metal hydride in the rate-determining step appears to involve substitution by an associative mechanism: [Eqn 4] Activation parameters for the reaction of [RhBr4(H20)2]⁻ with H2 are similar to those found for the corresponding reaction with CO (equation 1). The reaction of [Rh(C0)2Cl2]⁻ with 02 in 3M HC1 initiallyforms [RhIII(C0)C151]²⁻ by a path thought to involve formation of an oxygen complex: [Eqn 5] The observed kinetics indicate that further RhIII(CO) is autocatalytically produced according to the following sequence: [Eqn 6, 7, 8] Subsequent slower reaction to give chlororhodate(III) species 2-occurs via slow hydration of [Rh(C0)Cl5]²⁻. [Eqn 9,10] Studies on the oxidation of [Rh(CO)2C12]⁻ in LiCl/DMA by molecular 02 suggest the involvement of hydroperoxide free radicals for the production of RhII. Evidence for a carbonato intermediate formed during the oxidation process has been obtained. The RhII solutions were found to contain active, though inefficient, catalysts for the autoxida-tion of DMA. The presence of RhII - 02 has been detected by esr, and the superoxide species may be responsible for the autoxidation reaction. A paramagnetic chloride-bridged rhodium(II) anion [Rh0Clc(DMA)2]²⁻ was isolated from the oxygenated DMA solutions of [Rh(C0)2Cl2]⁻ containing excess chloride. / Science, Faculty of / Chemistry, Department of / Graduate

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