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Photoluminescent Zirconium Complexes For Visible Light Photoredox Catalysis, Yu Zhang Jan 2019

Photoluminescent Zirconium Complexes For Visible Light Photoredox Catalysis, Yu Zhang

Graduate Theses, Dissertations, and Problem Reports

Early transition metals like zirconium are attractive candidates for the design of luminescent molecules based on earth-abundant elements. Here, a series of zirconium complexes carrying two pyrrolyl-based ligands have been synthesized and characterized. These complexes are photoluminescent upon excitation with visible light and exhibit remarkably long emission lifetimes of hundreds of μs in solution at room temperature. Computational studies using time-dependent density functional theory (TD-DFT) were conducted to identify the nature of the luminescent excited states as mixed intra-ligand/ligand-to-metal charge-transfer (ILCT/LMCT) states. The electrochemistry studies revealed multiple reversible redox events for each zirconium complex. Furthermore, the excited state of the …


In Situ Infrared Spectroscopic Study Of Iron-Catalyzed Hydromagnesiation Of Vinyl Arenes, Jessica Ann Rogers Jan 2019

In Situ Infrared Spectroscopic Study Of Iron-Catalyzed Hydromagnesiation Of Vinyl Arenes, Jessica Ann Rogers

Graduate Theses, Dissertations, and Problem Reports

Iron catalysis, especially homogeneous catalysis, has been a resurging topic of organometallic chemistry research. Discussions of past and present mechanistic analyses for homogeneous iron catalysis will be discussed in Chapter 1. As an expansion of homogeneous iron catalysis, in situ infrared spectroscopy will be used to develop a full mechanistic study of iron-catalyzed hydromagnesiation of vinyl arenes. The kinetic analyses by both initial and observed rate measurements indicate complex concentration dependencies on the (PDI)iron catalyst as well as sacrificial Grignard reagent and styrene. These complexities are not limited to non-linear catalyst and Grignard initial rate and inhibition by styrene/Grignard at …


Copper-Catalyzed Regioselective Boracarboxylation Of Vinyl Arenes: Catalytic Efficiency And Synthetic Utility, Trina M. Perrone Jan 2019

Copper-Catalyzed Regioselective Boracarboxylation Of Vinyl Arenes: Catalytic Efficiency And Synthetic Utility, Trina M. Perrone

Graduate Theses, Dissertations, and Problem Reports

Hetero(element) carboxylation is an appealing transformation that involves the installation of CO2 and another hetero(element) in one step. This transition metal-catalyzed one-pot synthesis provides a route to achieve highly functionalized carboxylic acid products with an abundant and cheap C1 feedstock. This difunctionalization also avoids the use of reactive metal hydride species, which is a prominent limitation of hydrocarboxylation chemistry. A copper-catalyzed regioselective boracarboxylation of vinyl arenes has been developed to access pharmaceutically relevant β-boryl-α-aryl propionic acid products. One drawback of this reaction is the necessity for high catalyst loading to achieve catalytic turnover. To circumvent this issue, the reduction of …