Influence of Porous Materials on the Reactivity and Stability of Transition Metal Catalysts

Organometallic chemists have historically studied the influence of ligands and counteranions on homogeneous transition metal catalysts in order to improve their selectivities and reactivities. Recently, these interests have expanded to incorporate supramolecular hosts and heterogeneous porous materials as supports which can influence catalyst properties. This work encompasses such an integration of catalysts with heterogeneous supports, wherein two types of chiral porous materials are evaluated for their abilities to induce enantioselectivity with nano- and molecular- scale catalysts. Furthermore, the strategy of architectural stabilization is developed to improve a gold(III) catalyst via introduction into robust metal-organic frameworks.Chapter 1. A variety of catalysts were immobilized in chiral mesoporous silica, and their reactivities were evaluated. Efforts towards the enantioenrichment of MOF-520 are described. Additionally, a novel post-synthetic metalation strategy is described for the introduction of a transition metal catalysts into metal-organic frameworks via oxidative addition.Chapter 2. A novel architectural stabilization strategy is described with a structurally well- defined gold(III) catalyst in metal-organic frameworks. The robustness of IRMOF-10 and bio- MOF-100 were used to rigidify a gold(III) catalyst to suppress a unimolecular decomposition pathway – reductive elimination. Through this architectural stabilization strategy, decomposition of the incorporated gold(III) catalyst in the metal-organic frameworks was not observed; in contrast, the homogeneous analogue was prone to decomposition in solution. Stabilization of the gold(III) catalyst in these metal-organic frameworks precluded leaching and enabled recyclability, which is crucial for productive heterogeneous catalysis