Dempsey, Stephen2023-04-132023-04-132023-02https://hdl.handle.net/11299/253723University of Minnesota Ph.D. dissertation. February 2023. Major: Chemistry. Advisor: Steven Kass. 1 computer file (PDF); xx, 670 pages.Reactive ions are ubiquitous species in diverse areas of chemistry. Numerous studies have shown that cations paired with weakly coordinating anions can lead to potent and unexpected reactivity. In contrast, relatively little has been done with weakly coordinating cations paired with reactive anions. In the first part of this dissertation, current literature-standard weakly coordinating cations are examined and the synthesis and evaluation of new phosphonium cations is presented. Organocatalysis is a powerful component of the modern synthetic chemist’s toolbox. Previous work in the Kass group has shown that the inclusion of a positive charge onto acidic organocatalyst motifs leads to potent reactivity enhancements. The latter half of this dissertation discusses the inverse, where an anionic center was included on a basic pyridine moiety and the resulting electrostatically enhanced base organocatalysts reactivity was examined. Additionally, an exploration of the ionic structure of the most potent catalysts via a variety of methods is presented.enionsorganic chemistryorganocatalysisThesis or Dissertation