Improvements to the Crystalline Sponge Method and Forays into Innovative Catalyst Design
Waldhart, Greyson Wayne
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Chapter 1 introduces the concept of the crystalline sponge method by first discussing the history and importance of X-ray crystallography, an overview of supramolecular chemistry, and the applications of MOFs. With this background information established, a comprehensive overview of the crystalline sponge method is described. This method provides a path for elucidating the structure of a small molecule without synthesizing a crystalline sample. The crystalline sponge method has already been proven to make significant contributions to the structure determination of natural products, unstable molecules, and chiral molecules. Chapter 2 describes the improvements we have made to the crystalline sponge method. The current technology is not compatible with a wide range of substrates and there is a very low probability of collecting good quality data. We developed an improved procedure that provides a higher percentage of good quality crystals and shortens the amount time required to prepare a crystal for guest inclusion. We then created a comprehensive list of MOF materials that could be probed as candidates for the crystalline sponge method by searching through the CSD. Chapter 3 discusses how we developed an iron-catalyzed Heck coupling of benzyl chlorides and styrenes proceeds under photochemical conditions using the well-known anionic complex, [FeCp(CO)2]- (Fp-), as a catalyst. We determined that the reaction likely proceeds through the established SN2 mechanism for Fp- alkylation, followed by styrene migratory insertion and β-hydride elimination steps that are enabled by photochemical CO dissociation. Chapter 4 communicates advances that were made towards the application of late-late heterobimetallic catalysts. We widened the library of heterobimetallic complexes by synthesizing and characterizing Ag and Au analogues. Then we analyzed the compatibility of heterobimetallic complexes toward novel organic reactions including: C–C coupling, N2O oxygen transfer, difunctionalization reactions, silaboration, hydroboration, and hydrosilation. Even though we were unable to discover any catalytic reactions, we did learn about some interesting stoichiometric reactivity that improved our understanding of how our catalysts work. Chapter 5 provides all experimental procedures for the chemical procedures and data work up processes for chapters 2–4. The chapter contains procedures and data from all published work as well as the synthesis of unpublished complexes and the procedures for any failed experiments.
Base Metal Catalysis