Thesis (PhD)--University of South Australia, 1996

Thesis (Ph.D.)--McMaster University, 2005. / Supervisor: William J. Leigh. Includes bibliographical references. Also available online.

The temperature dependence of the reactions of halogen atoms Cl and Br with SiH4 and (CH3)3SiH have been investigated with the flash photolysis-resonance fluorescence technique. CCI4 and CH2Br2 were used as precursors to produce Cl and Br atoms, respectively. Experiments gave {k(Cl + SiH4) (295 - 472 K)} = (1.56 +0.11) x 10-1 exp[(2.0 + 0.2) kJ mol'/RT] cm3 s4, {k(Br + SiH4)(295 - 575 K)} = (9.0 + 1.5) x 10-" exp[-(17.0 + 0.6) Id mol'/RT] cm3 s', {k(Cl + (CH3)3SiH)(295 - 468 K)} = (1.24 0.35) x 104 exp[(1.3 + 0.8) Id mol4/RT] cm3 s', and {k(Br + (CH3)3SiH)(295 - 456 K)} = (7.6 + 3.3) x 1010 exp[-(28.4 + 1.3) Id mol'/RT] cm3 s'. The results were compared with values from earlier work.

M.S.

Part I. The syntheses of a series of stable ferrocenylsilane compounds and their corresponding polyradical cations are reported. Electron spin properties of these molecules were investigated by cyclic voltammetry, ESR, and magnetic susceptibility measurements. All the compounds presented, showed significant electronic communication (>100 mV) between the redox centers by CV. Part II. Baeyer-Villiger oxidation of (1,9-dimethyl-PCU-8,11-dione) was performed using m-chloroperoxybenzoic acid in 1:2 molar ratios. The product obtained was the corresponding dilactone 113. The structure of the reaction products was established unequivocally via single crystal X-ray diffraction methods. The reaction of the 1,9-dimethyl-PCU-8,11-dione with 1:1 molar ratio of m-chloroperoxybenzoic acid produced again the dilactone 113, and not the expected monolactone 114. Ceric ammonium nitrate (CAN) promoted oxidation reaction of 1,9-dimethyl-PCU-8,11-dione afforded a mixture of dimethylated lactones, which indicated unique reaction mechanism pathways. These individual isomers, 115 and 116, have been isolated from these mixtures via column chromatography by using silica gel as adsorbent followed by fractional recrystallization of individual chromatography fractions. Structures of these pure products have been established unequivocally by application of single crystal X-ray crystallographic methods.

This research focuses on carbon fiber treatment by nitric acid and 3- (trimethoxysilyl)propyl methacrylate silane, and how this affects carbon/vinyl ester composites. These composites offer great benefits, but it is difficult to bond the fiber and matrix together, and without a strong interfacial bond, composites fall short of their potential. Silanes work well with glass fiber, but do not bond directly to carbon fiber because its surface is not reactive to liquid silanes. Oxidizing surface treatments are often prescribed for improved wetting and bonding to carbon, but good results are not always achieved. Furthermore, there is the unanswered question of environmental durability. This research aimed to form a better understanding of oxidizing carbon fiber treatments, determine if silanes can be bonded to oxidized surfaces, and how these treatments affect composite strength and durability before and after seawater exposure. Nitric acid treatments on carbon fibers were found to improve their tensile strength to a constant level by smoothing surface defects and chemically modifying their surfaces by increasing carbonyl and carboxylic acid concentrations. Increasing these surface group concentrations raises fiber polar energy and causes them to cohere. This impedes wetting, resulting in poor quality, high void content composites, even though there appeared to be improved adhesion between the fibers and matrix. Silane was found to bond to the oxidized carbon fiber surfaces, as evidenced by changes in both fiber and composite properties. The fibers exhibited low polarity and cohesion, while the composites displayed excellent resin wetting, low void content, and low seawater weight gain and swelling. On the contrary, the oxidized fibers that were not treated with silane exhibited high polarity and fiber cohesion. / Their composites displayed poor wetting, high void content, high seawater weight gain, and low swelling. Both fiber treatment types resulted in great improvements in dry transverse tensile strength over the untreated fibers, but the oxidized fiber composites lost strength as the acid treatment time was extended, due to poor wetting. The acid/silane treated composites lost some transverse tensile strength after seawater exposure, but the nitric acid oxidized fiber composites appeared to be more seawater durable. / by Tye A. Langston. / Thesis (Ph.D.)--Florida Atlantic University, 2008. / Includes bibliography. / Electronic reproduction. Boca Raton, Fla., 2008. Mode of access: World Wide Web.

*Please refer to dissertation for diagrams. / Part I describes the silicon-hydrogen bond activation (SiHA) of silanes with both electron-deficient iridium porphyrin carbonyl chloride (Ir(ttp)Cl(CO)) and electron-rich iridium porphyrin methyl (Ir(ttp)Me) to give iridium(III) porphyrin silyls (Ir(ttp)SiR3). Firstly, Ir(ttp)SiR3 were synthesized in moderate to good yields conveniently from the reactions of Ir(ttp)Cl(CO) and Ir(ttp)Me with silanes, via SiHA in solvent-free conditions and non-polar solvents at 200°C. Base facilitated the SiHA reaction even at lower temperature of 140°C. Specifically, K3PO4 accelerated the SiHA with Ir(ttp)Cl(CO), while KOAc promoted the SiHA by Ir(ttp)Me. Mechanistic experiments suggest that Ir(ttp)Cl(CO) initially forms iridium porphyin cation (Ir(ttp)+), which then reacts with silanes likely via heterolysis to give iridium porphyrin hydride (Ir(ttp)H). Ir(ttp)H further reacts with silanes to yield Ir(ttp)SiR3. On the other hand, Ir(ttp)Me and Ir(ttp)SiR3 undergo either oxidative addition (OA) or sigma-bond metathesis (SBM) to form the products. In the presence of base, a penta-coordinated silicon hydride species likely forms and reacts with Ir(ttp)Me to form iridium porphyrin anion (Ir(ttp) -) that can further react with silane to yield Ir(ttp)H after protonation. Ir(ttp)H finally reacts with excess silane to give Ir(ttp)SiR 3.* / Part II describes successful base promoted aromatic carbon-fluorine (C-F) and carbon-hydrogen (C-H) bond activation of fluorobenzenes in neat conditions to give the corresponding iridium(III) porphyrin aryls (Ir(ttp)Ar) at 200°C in up to 95% yield. Mechanistic studies suggested that Ir(ttp)SiEt3 is firstly converted to Ir(ttp)- in the presence of KOH. Ir(ttp)- cleaves the aromatic C-F bond via an S NAr process. As the reaction proceeds, a hydroxide anion can coordinate to the iridium center of Ir(ttp)Ar to form an iridium porphyrin trans aryl hydroxyl anion (trans-[ArIr(ttp)OH]-). In the presence of water, trans-[ArIr(ttp)OH]- can give Ir(ttp)OH and ArH. Ir(ttp)OH then undergoes aromatic C-H bond activation reaction to give Ir(ttp)Ar'. Furthermore, the aromatic C-F bond activation products were found as the kinetic products, and aromatic C-H bond activation products were the thermodynamic ones.* / Part III describes the successful C(C=O)-C(alpha) bond activation of acetophenones by high-valent iridium porphyrin complexes (Ir(ttp)X, X = Cl(CO), (BF4)(CO), Me) in solvent-free conditions at 200°C to give the corresponding iridium porphyrin benzoyls (Ir(ttp)COAr) in up to 92% yield. Mechanistic studies suggest that Ir(ttp)X reacts with acetophenones to give alpha-CHA product as the primary product, which can re-convert back to the active intermediate Ir(ttp)OH or Ir(ttp)H in the presence of water formed from the concurrent iridium-catalyzed aldol condensation of acetophenones. Then Ir(ttp)OH cleaves the aromatic C-H bonds to produce the aromatic CHA products, which are more thermally stable than the alpha-CHA product. Both Ir(ttp)H and Ir(ttp)OH were the possible intermediates to cleave the C(C=O)-C(alpha) bond to give thermodynamic products of Ir(ttp)COAr. On the other hand, only Ir(ttp)(BF 4)(CO) can react with the aliphatic ketones, likely due to the stronger Lewis acidity and the HBF4 generated in catalyzing the aldol condensation of aliphatic ketones to facilitate the formation of Ir(ttp)OH and Ir(ttp)H.* / The objectives of the research focus on the bond activation chemistry by iridium porphyrin complexes with three organic substrates, (1) hydrosilanes (HSiR3), (2) fluorobenzenes (C6HnF6-n , n = 0--6), and (3) aromatic or aliphatic ketones (RCOR, R = alkyl or aryl). / Li, Baozhu. / Adviser: Kin Shing Chan. / Source: Dissertation Abstracts International, Volume: 72-01, 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 Company, [200-] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstracts in English and Chinese.

Thesis (Ph. D.)--Ohio State University, 2006. / Full text release at OhioLINK's ETD Center delayed at author's request

This thesis focuses on the development of new compounds or new processes that are more environmentally friendly and economical than those currently in use. The decomposition of hydrazine, a well established liquid rocket fuel for both the aerospace and defense industries, to the product ammonia is studied. Control of this reaction will allow hydrazine to be used as a propellant for both chemical and electric propulsion. From this a dual stage thruster will be developed that will be more efficient than current systems decreasing the amount of propellant needed and allowing for either a larger mission payload or a longer duration of individual missions. Hydrazine, while beneficial and well established, is also highly toxic, so other work in this thesis focuses on the synthesis of the novel molecule 1,1-dimethyl-2-[2-azidoethyl]hydrazine or DMAEH and its hydrazone intermediate 1,1-dimethyl-2-[2-azidoethyl]hydrazone or De-DMAEH as less toxic hydrazine replacements. Novel "switchable" ionic liquids have been investigated in this research. These are solvents that can change from molecular liquids to ionic liquids and back, simply with the addition or removal of CO₂ from the system. They can be used for a variety of applications, including as solvents for a reaction and separation system. Due to the recyclable nature of these solvents, waste is decreased making their development and implementation both environmentally and economically beneficial. Finally, the grafting reaction of vinyl silanes onto a hydrocarbon backbone is investigated. Fundamental work is being performed to study the graft distribution, selectivity and mechanism by which this reaction occurs. A more thorough understanding of how this reaction proceeds will allow for the development of a more efficient industrial process.

Cross-linked polyethylene has higher upper use temperature than normal polyethylene and is used as an insulating material for electricity carrying cables and hot water pipes. The most common method of inducing crosslinks is by reaction with silanes. After incorporation of silanes into polyethylene and upon hydrolysis with ambient moisture or with hot water, Si-O-Si crosslinks are formed between the various linear polyethylene chains. Industrially, this reaction is performed routinely. However, the efficiency of this reaction with respect to the silane is low and control of product distribution is difficult. A precise fundamental understanding is necessary to be able to manipulate the reactions and thus, allow for the facile processing of the polymers. Hydrocarbon models of polymers - heptane, dodecane - are being used to study this reaction in the laboratory. For the reaction, vinyltrimethoxysilane is used as the grafting agent along with di-tert-butyl peroxide as the radical initiator. MALDI, a mass spectrometric technique is used for the analysis of the product distribution after work-up. Advanced NMR techniques (COSY, HSQC, DEPT, APT, HMBC) are being conducted on the grafted hydrocarbon compounds to gain an in-depth understanding of the mechanism and regiochemistry of the grafting reaction. Scalable and cost effective methods to capture CO2 are important to counterbalance some of the global impact of the combustion of fossil fuels on climate change. The main options available now include absorption, adsorption and membrane technology. Amines, especially monoethanolamine, have been the most commercialized technology. However, it is not without disadvantages. House et al have investigated the energy penalty involved in the post-combustion CO2 capture and storage from coal-fired power plants and found that 15-20% reduction in the overall electricity usage is necessary to offset the penalty from capturing and storing 80% of United States coal fleet's CO2 emssions1. Novel non-aqueous amine solvents, developed by the Eckert Liotta group, react with CO2 to form ionic liquids. The ionic liquids readily desorb CO2 upon heating, regenerating the reactive amines and this cycle can be carried out multiple times. An iterative procedure is being adopted to develop amine solvents for CO2 capture. Thermodynamic information like reversal temperature and boiling point of the solvents are collected; they are then used to formulate structure property relationships which allow for new molecules to be engineered. On reaction with CO2, there is a sharp increase in viscosity which is unfavorable from a processing standpoint. Many approaches to mitigate and control viscosity are being studied as well. 1House et al, Energy Environ Sci, 2009, 2, 193-205