A series of cyclometalated gold(III) complexes with N-heterocyclic carbine (NHC) or alkynyl as auxiliary ligand were synthesized and characterized. Complexes [AuIII(R1 –C^N^C)(NHC)](OTf) and [AuIII(C^N^C)(C≡CR2)] (HC^N^CH = 2,6-di(naphthalene-2-yl)pyridine; R1 = H or 4-methoxyphenyl; R2 =aryl) are emissive in solution at room temperature with quantum yields in the range of 0.65–11.4% and lifetimes ranging from 98 to 506 s. [AuIII(4-(4-OMePh)–C^N^C)(NHC)](OTf) showed prominent photochemical properties. This complex effectively catalyses photo-induced oxidation of secondary amines (to the corresponding imines) and -functionalization of tertiary amines in good to excellent yields; it also acts as a photosensitizer for hydrogen generation in a water/acetonitrile mixture, producing more than 350 turnovers of hydrogen after 4 hours of irradiation. Palladium(II) meso-tetrakis(pentafluorophenyl)porphyrin was found to be an efficient and robust catalyst for the photo-induced oxidative C–H bond functionalization reactions. Several kinds of -functionalized tertiary amines were obtained in good to excellent yields by irradiating a mixture of palladium(II) catalyst, corresponding tertiary amine and nucleophile under aerobic conditions. The nucleophiles for these reactions include cyanide, nitromethane, dimethyl malonate, diethyl phosphite and acetone. Two examples of novel intramolecularly cyclized amines were also described. Comparison of the UV-vis absorption spectra before and after reaction indicated that the palladium catalyst was highly robust. The practical potential of this catalyst was shown by the success in reactions at a low catalyst loading and on a large scale. The palladium(II) catalyst could also sensitize photo-induced oxidation of sulfide to sulfoxide and photo-induced hydrogen production in a water/acetonitrile mixture with up to 240 turnovers. [FeIII(L-N4Me2)Cl2][FeCl4] (L-N4Me2 = N,N’-dimethyl-2,11-diaza[3,3] (2,6)pyridinophane) was demonstrated to be an active catalyst for water oxidation. When cerium ammonium nitrate (CAN) was used as the oxidant, the iron(III) catalyst oxidized water to oxygen with up to 93 turnovers after 30 minutes in 0.1 M nitric acid, whereas changing the oxidant to sodium periodate (NaIO4) resulted in only 44 turnovers of oxygen after 30 minutes. The mechanism of the reaction was explored by high resolution electrospray ionization mass spectrometry (ESI-MS), 18O labeling, UV-vis absorption spectroscopy, kinetic plots and DFT calculations. In the case of using CAN, an FeIV-oxo species was detected by ESI-MS and UV-vis absorption spectroscopy. The rate of oxygen evolution was found to be linearly dependent on both concentrations of catalyst and oxidant. 18O labeling studies confirmed that the origin of oxo ligands was from water and was irrespective of the choice of oxidant. This reaction was proposed to involve a coupling between an FeIV-oxo species and a hydroxocerium(IV) radical. In the case of using NaIO4, an FeV-dioxo species was detected by ESI-MS as a major species, and a small amount of FeIV-oxo species was detected by UV-vis absorption spectroscopy. As the rate of oxygen evolution was found to be linearly dependent on the concentration of catalyst only, the reaction was proposed to involve a cis-FeV-dioxo species. DFT calculations showed that the cis-FeV-dioxo species was capable of oxidizing water to oxygen through the formation of an [FeIII(L-N4Me2)(OO?)(OH)]+ intermediate. / published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

Thesis (Ph.D.)--Hong Kong University of Science and Technology, 2006. / Includes bibliographical references. Also available in electronic version.

Thesis (M.S.)--University of Florida, 2004. / Title from title page of source document. Document formatted into pages; contains 60 pages. Includes vita. Includes bibliographical references.

Thesis (Ph. D.)--University of North Texas, Dec., 2007. / Title from title page display. Includes bibliographical references.

Thesis (Ph. D.)--University of Oregon, 2008. / Typescript. Includes vita and abstract. Includes bibliographical references (leaves 195-204). Also available online in ProQuest, free to University of Oregon users.

Thesis (Ph. D.)--West Virginia University, 2010. / Title from document title page. Document formatted into pages; contains xii, 328 p. : ill. (some col.). Includes abstract. Includes bibliographical references (p. 81-91).

Submitted in fulfillment of the requirements for the Master of Engineering Degree, Durban University of Technology, Durban, South Africa, 2018. / Ethanol and butanol obtainable through fermentation of lignocellulose biomass have become promising alternative feedstock for production of fuels as they are biodegradable and sustainably regenerated via the photosynthesis cycle. The properties of hydrocarbons produced through alcohol conversion closely resemble those of gasoline. Catalytic systems are reported to play a vital role during alcohol conversion to hydrocarbons. In this study ethanol and butanol were used as a feedstock for production of hydrocarbons over Fe, Zn and Ni catalyst systems supported on zeolite ZSM-5 (Zeolite Socony Mobil-5) and activated carbon (AC). X- Ray Diffraction (XRD), Scanning Electron Microscope (SEM) coupled with Energy- dispersive X-ray spectroscopy (EDS) and Brunauer, Emmet, and Teller (BET) analyses were employed for catalyst characterization. XRD patterns confirmed the success of metal doping on ZSM-5 and activated carbon supports. Major peaks at 7.96° and 23.97° corresponding to ZSM-5 crystals were observed in ZSM-5, and AC was found to be amorphous. Impregnation with metals reduced the crystallinity of ZSM-5 supported catalysts. Whereas SEM analysis showed that catalysts supported on ZSM-5 exhibited irregular shapes and catalyst supported on activated carbon exhibited disordered structures. The BET analyses confirmed that the surface areas of promoted catalysts decreased after metal doping. Evaluation of the catalysts were carried out in a ½ inch stainless steel reactor at 400 °C and atmospheric pressure with a weight hourly space velocity (WHSV) of 2.5 h-1 (g feed)/ (g catalyst). The ZSM-5 support performed better than activated carbon support. More than 90% conversion was achieved over catalysts supported on ZSM-5. Production of hydrocarbons over catalysts supported on activated carbon were as a result of the active component. Conversion of feedstock was observed to produce more benzene, toluene and xylene (BTX) compounds with an increase in butanol content. 100% conversion was achieved with pure butanol and not more than 99.86% conversion was achieved with pure ethanol. Catalyst systems supported on HZSM-5 and activated carbon were successfully synthesised. Ethanol, butanol and ethanol-butanol mixtures were successfully converted to liquid hydrocarbons and the conversion was greater than 90%. On the promoted catalysts, production of BTX were suppressed and various metals were observed to perform differently. / M

Thesis (Ph. D.)--University of Wyoming, 2006. / Title from PDF title page (viewed on Dec. 20, 2007). Includes bibliographical references.

Chapter 1 reviews the relevant and particularly interesting chemistry of C₆₀ and includes some chemical aspects of the other recently discovered new forms of carbon including the graphitic carbon nanotubules, concentric carbon spheres and amorphous carbon networks. An experimental section describes the techniques used for the synthesis of fullerene rich soot and the subsequent isolation and purification of C₆₀ as performed in the Inorganic Chemistry Laboratory, Oxford. Chapter 2 describes the synthesis, characterisation, and some reaction chemistry of the new complex Rh(η²-C₆₀)(CO)(H)(PPh₃)₂ and its activity with respect to the catalytic hydroformylation of ethene and propene, and is compared to the industrially used catalyst Rh(CO)(H)(PPh₃)₃. Studies to determine the thermal stability of Rh(η²-C₆₀)(CO)(H)(PPh₃)₂ compared to Rh(CO)(H)(PPh₃)₃ during hydroformylation catalysis are also included. Chapter 3 describes the synthesis and characterisation of the new complexes NaC₆₀.5thf, NMe₄C₆₀.1.5thf and what could be the new complex Na_0.9C₆₀.3thf. These materials exhibit a magnetic transition at approximately 180K as determined by bulk static D.C. susceptibility measurements and electron spin resonance spectroscopy. This transition is discussed mainly in terms of a metal-metal or metal-insulator transition. Some reaction chemistry of these materials is also described. Also described are studies into various aspects of the sodium C₆₀ phase diagram at ambient temperature and pressure with regard to the proposed solid solution behaviour in the compositional range Na₁C₆₀ to Na₃C₆₀. The synthesis of the novel hexagonal close packed compounds Na₆C₆₀ and Na₉C₆₀ and consequences for the phase diagram of sodium C₆₀ intercalates are discussed. Chapter 4 describes the synthesis of various alkali metal C₆₀ intercalates using a microwave induced argon plasma as the heat source. The developement of this technique for the bulk synthesis of other materials and attempts at the synthesis of novel lithium and ytterbium intercalates are also described.

Thesis (Ph.D.) -- McMaster University, 2001. / Includes bibliographical references. Also available via World Wide Web.