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. 

Abstract: Atmosphere aerosols, including secondary organic aerosols (SOA), are ubiquitous constituents in the atmosphere. During their lifetimes, these aerosols can be transported hundreds of kilometers from their source and can undergo a variety of chemical and physical changes depending on the atmospheric conditions (e.g., acidity). However, SOA formation and aging processes--including the influence of acidity on these processes--are the leading source of uncertainty in aerosol radiative forcing in global climate models.

Abstract: During this thesis defense I will describe my work in the synthesis, isolation, characterization, and application of a Ru-MACHO® derived dihydride complex that displays CO2-reduction activity. Research efforts focused on decreasing the impact of CO2 emissions must work to design processes that generate high-value products without requiring a high input of energy. One method that addresses this concern is combined CO2 capture and CO2 conversion, where electrochemistry can be utilized to perform CO2 conversion under mild conditions.

Abstract: Traditional methods to perform cyclopropane synthesis typically utilize carbenoid intermediates or other nucleophiles reacting with olefins to form two C–C bonds in a single reaction. In order to expand the chemical space of these syntheses, it is necessary to find orthogonal techniques that offer new ways to access similar products and stereochemical outcomes as these methods. One way to accomplish this is by using alcohols, one of the most prevalent functional groups in chemistry, as a starting material.