Preparation, Characterization, and Reactivity of Ruthenium Protic N-Heterocyclic Carbene Complexes
|Institution:||University of Washington|
|Full text PDF:||http://hdl.handle.net/1773/40862|
As carbon dioxide levels continue to rise in our atmosphere, scientific interest has peaked around the capture and utilization of CO2. Not only does CO2 have the potential to be used as a C1 building block for the production of value added chemicals, but CO2 also has the potential to be used as a carbon neutral hydrogen storage material in the form of formic acid. Although catalysts for CO2 reduction exist, many of these catalysts require the use of high temperatures and pressures and are not stable for prolonged exposure to the reaction conditions. Therefore, the challenge of making robust catalysts for CO2 hydrogenation that can operate under mild conditions with high activity remains outstanding. With the goal of generating a robust and highly active CO2 hydrogenation catalyst in mind, this thesis describes the fundamental metalation chemistry of a novel tripodal bis(protic N-Heterocyclic carbene)-phosphine ligand with ruthenium precursors and the reactivity of the resulting organometallic complexes with CO2. Chapter 1 provides a brief overview of CO2 in the earths atmosphere, a glimpse at CO2 hydrogenation chemistry, and an introduction to traditional and protic N-heterocyclic carbene (PNHC) chemistry. Chapter 2 describes the synthesis and characterization of PNHC Ru complexes utilizing [Cp*RuCl]4 as the ruthenium precursor. Chapter 3 investigates the coordination chemistry and synthesis of PNHC Ru complexes stemming from [(Arene)Ru] precursors. Chapter 4 describes both stoichiometric and catalytic reactivity studies of complexes synthesized in Chapters 2 and 3 with CO2. Finally, Chapter 5 dives into an entirely new subject and discusses the crystallographic structure determination of an unprecedented In37P20 nanocluster.Advisors/Committee Members: Cossairt, Brandi M (advisor).