Dereli, Busra2018-09-212018-09-212018-06https://hdl.handle.net/11299/200205University of Minnesota Ph.D. dissertation. June 2018. Major: Chemistry. Advisor: Christopher Cramer. 1 computer file (PDF); xiv, 134 pages.As many key elementary reactions having broad utility in chemistry have been found to be catalyzed at transition-metal centers, there has been enormous effort devoted to the design and optimization of such catalysts. In addition to empirical experiments that measure catalytic activity, theoretical chemistry offers a complementary approach to understanding mechanisms of catalysis and can be used to accelerate the design of second- and subsequent-generation catalysts with further improved properties. In the broader sense, catalysis science provides opportunities to explore and understand how catalysts work at the atomic scale by means of computation, synthesis, and characterization. The primary goal of this thesis to investigate the fundamental features of transition-metal-based systems and their roles in the activation mechanisms of hydrocarbon and biomass feedstocks via density functional theory (DFT) and wave function (WF) theory methods. Accordingly, this thesis presents (i) accurate prediction of gas-phase ionization energies of mononuclear copper complexes using high level quantum mechanical methods (Chapter 2), (ii) the effects of electronic perturbations on the copper-hydroxide complexes involved in C-H bond activation reactions (Chapter 3), (iii) catalytic decarbonylation of biomass-derived carboxylic acid derivatives to olefins (Chapter 4), (iv) the dual ligand role in selective decarbonylation of fatty-acid esters to linear α-olefins (Chapter 5).enCatalysisChemical TransformationsDensity Functional TheoryTransition-metal complexesWave Function TheoryThesis or Dissertation