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Nickel(0) Catalyzed Carbon-Hydrogen Bond Activation: A Mechanistic Study Of The Formation Of A Nickel(I)-Nickel(I) Complex., Alana Lauren Keen
Nickel(0) Catalyzed Carbon-Hydrogen Bond Activation: A Mechanistic Study Of The Formation Of A Nickel(I)-Nickel(I) Complex., Alana Lauren Keen
Electronic Theses and Dissertations
The first part of this thesis deals with a mechanistic investigation into the conversion of the known benzyne complex, Ni(eta2-C 6H2F2)(PEt3)2, to the novel dinuclear Ni(I)-Ni(I) complex, (PEt3)4Ni2(eta 2-C6H2-4,5-F2)2. The coupling of two molecules of Ni(eta2-C6H2F 2)(PEt3)2 does not result in the formation of (PEt3)4Ni2(eta2-C6 H2-4,5-F2)2. There is a rearrangement in the disposition of the hydrogen atoms from para disposed in Ni(eta 2-C6H2F2)(PEt3)2 to ortho disposed in (PEt3)4Ni2(eta 2-C6H2-4,5-F2)2, which was found to be the result of C-H bond activation catalyzed by Ni(0). Proposed mechanisms involving the isolated reaction intermediates Ni2(mu-eta 2:eta2-C6H2F2)(PEt 3)2 and (PEt3)2(PMe3) 2Ni2(eta2-C6H2-3,4-F 2)2 are given and …
Studying The Anti-Cancer Potential Of The Natural Compound Pancratistatin., Amanda Mclachlan-Burgess
Studying The Anti-Cancer Potential Of The Natural Compound Pancratistatin., Amanda Mclachlan-Burgess
Electronic Theses and Dissertations
One of the current challenges in the fight against cancer is to find anti-cancer treatments that specifically target cancerous cells, while leaving normal cells unharmed. Apoptosis, or programmed cell death, is a non-traumatic, physiological process by which cells that are no longer needed or are potentially harmful can be removed from the system. Recently, anti-cancer research has focused on targeting the components of biochemical pathways that can induce apoptosis specifically in cancerous cells. The search for cancer-specific drugs has led some researchers to investigate the potential anti-cancer activity of natural compounds. Pancratistatin (PST) is a natural compound that was isolated …
Syntheses And Reactivities Of Improved Univalent Indium Salts., Christopher G. Andrews
Syntheses And Reactivities Of Improved Univalent Indium Salts., Christopher G. Andrews
Electronic Theses and Dissertations
Reported herein are the syntheses and characterizations for a number of new families of compounds containing the main group metal indium in its relatively uncommon univalent oxidation state. Starting from the known half-sandwich compound Cp*In, (Cp* = pentamethylcyclopentadienyl) it is possible to effect a clean and facile cleavage of the organic ring from the metal with the addition of a non-oxidizing Bronstead acid. Once removal of the hydrocarbon by-product is accomplished, the metal is left in a binary salt with the conjugate base of the Bronstead acid used. This protonolysis approach is a versatile method allowing for easy selection of …
Anion Interactions Of [2]Pseudorotaxanes And [2]Rotaxanes., Iavor S. Mihalkov
Anion Interactions Of [2]Pseudorotaxanes And [2]Rotaxanes., Iavor S. Mihalkov
Electronic Theses and Dissertations
This thesis describes studies on the interactions of anions with [2]pseudorotaxanes and [2]rotaxanes comprised of 24-membered crown ether wheels and bis(pyridinium)ethane axles which incorporate an amide anion receptor. Eight nicotinamide-based threads containing a bis(pyridinium)ethane recognition motif were synthesized. Their ability to form [2]pseudorotaxane complexes with 24-membered crown ethers was determined by 1H NMR spectroscopy. The effect of anion binding on the stability of the [2]pseudorotaxanes was investigated using 1H NMR titrations. Nine [2]rotaxanes were synthesized from the combination of three threads and three crown ethers---dibenzo-, dinaphtho-, and naphtho-24-crown-8. The selectivity of the amide receptor towards small inorganic anions---halides and dihydrogenphosphate---were …
Nonlinear Instabilities In Photochemical Oxidations Of 1,4-Cyclohexanedione And Its Derivatives., Bei Zhao
Nonlinear Instabilities In Photochemical Oxidations Of 1,4-Cyclohexanedione And Its Derivatives., Bei Zhao
Electronic Theses and Dissertations
In the closed 1,4-cyclohexanedione(CHD) bromate oscillatory reaction, we discovered that stirring can induce transitions between simple and period-doubled oscillations. When illumination was employed to characterize the importance of micro fluctuations of concentrations, the threshold stirring rate for inducing a bifurcation was found to increase proportionally to the intensity of the applied light. Numerical simulations with an existing model illustrate that the experimental phenomena could be qualitatively reproduced by considering effects of mixing on diffusion-limited radical reactions, namely, the disproportion reaction of hydroquinone radicals. A novel light-mediated chemical oscillator, i.e. 1,4-benzoquione(Q-bromate oscillator, was uncovered and investigated systematically in a batch reactor. …