Abstract:

Abstract:  

Abstract: Catalysis remains an important field of research that drives economical approaches for various energy conversion applications from natural resources. Industrial catalyzed reactions occur at the surface of heterogeneous catalysts where many different active sites exist. Any atom not at the surface is not directly used to drive chemical reactions. To improve efficiency, catalytic materials have shrunk to the nano and atomic scale, increasing the surface area/volume ratio.

Abstract: This dissertation describes efforts to expand the area of low oxidation state chemistry for the rare-earth metals and the actinides. The use of the spherically encapsulating 2.2.2-cryptand (crypt) for the isolation of new complexes of +3 and +2 ions of these metals was explored. In addition, X-ray photoelectron spectroscopy (XPS) was used to evaluate the electron configurations of Gd(II) complexes by comparison with Gd(III) analogs.

Abstract: The first segment of this presentation will detail our development of a methodology to control π-facial selectivity in intramolecular Diels–Alder cyclizations using a silacycle directing group. A panel of substrates is synthesized and tested, providing insight into the capabilities and, more importantly, the limits of the methodology. Deeper mechanistic insight is gained through a deuterium-labelling study, which suggests the role of [1,5] hydride shifts in the formation of the reactive diene.