Date of Award
Doctor of Philosophy
The investigation and development of heterobimetallic systems has seen a meteoric surge over the past decade. Generally, these heterobimetallic systems involve two transition metals with distinct properties used together to activate chemical bonds. Many heterobimetallics consist of a soft, low-valent metal and a harder, high-valent metal. The unique electronics afforded by heterobimetallics of this sort can be exploited, yielding access to novel reactivities that may be otherwise inaccessible to a single transition metal. Less studied are heterobimetallic complexes composed of one late transition metal (LTM) and one Lewis-acidic p-block (Group 13) metal. Due to its electropositivity being the highest among Group 13 metals as well as its high earth-abundance, aluminum holds particular interest to the Brewster laboratory. In contrast to their exhaustively investigated boron analogues, the field of aluminum-containing heterobimetallics is relatively uncultivated due to the high reactivity and synthetic difficulty of aluminum species, making isolation and characterization quite challenging. One of the aims of the Brewster lab is to develop heterobimetallic systems comprised of an electron-rich, low-valent transition metal and aluminum to investigate potential synergistic reactivity between both metal centers. In this dissertation, I report the successful synthesis and electronic characterization of myriad novel mono- and heterobimetallic complexes of either iridium or rhodium and aluminumover 35 new complexes in total. Moreover, I detail the ability of selected heterobimetallic complexes to facilitate activation of molecular hydrogen as well as hydrogenolysis, thereby generating alkane gas.
Dissertation or thesis originally submitted to ProQuest
Charles III, Roland Malcolm, "Synthesis, Characterization, and Reactivity Evaluation of Late Transition Metal-Aluminum Heterobimetallic Complexes Toward Molecular Hydrogen" (2021). Electronic Theses and Dissertations. 2491.