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  • Intrazeolite chemistry of b...
    Ogunwumi, Steven Bolaji

    01/1997
    Dissertation

    In ongoing efforts to develop new catalytic applications involving zeolites, heteronuclear bimetallic complexes were synthesized and anchored in zeolites. The intrazeaolite reactivity of these complexes were studied using various techniques such as Extended X-ray Absorption Fine Structure Spectroscopy (EXAFS), Fourier Transform Infrared-Temperature Programmed Desorption-Mass spectroscopy (FTIR-TPD-MS), and UV-Vis spectroscopy. Results obtained from investigating the reactivity of these systems are reported along with their catalytic activity. In another effort, we report successful incorporation of a chiral Manganese(III) salen complex in hexagonal faujasite zeolite (EMT). Due to the size and rigidity of the chiral complex after synthesis inside the zeolite, it is physically entrapped inside the zeolite pore structure "(Ship in a Bottle)." The resulting heterogenous system was simulated using molecular modeling and then physically characterized using a variety of analytical techniques. These techniques include XRF (X-ray Fluorescence), diffuse reflectance UV/VIS, ESR (Electron Spin Resonance), FTIR Spectroscopy and Nitrogen Adsorption Analysis. Various prochiral olefins were used to probe the heterogenous catalytic activity of this system in asymmetric epoxidations. The highest enantiomeric excess (ee) obtained was 80% for cis-$\beta$-methylstyrene oxide. Experimental evidence indicates that the encapsulated complex does not leach.