Date of Award


Degree Type


Degree Name

Doctor of Philosophy (PhD)

Graduate Group


First Advisor

Karen I. Goldberg


Selective functionalization of hydrocarbons into higher-value products would reduce the environmental impacts currently associated with the petrochemical industry. Using a green oxidant, such as dioxygen, to effect these oxidation/oxygenation reactions would also be environmentally beneficial. This dissertation reports results aimed at furthering the understanding of key fundamental reaction steps in proposed catalytic cycles of aerobic alkane activation using Pt and Pd complexes. To this end, a series of tridentate nitrogenous ligands have been synthesized and ligated to Pt and Pd. New binding modes have been observed and the general advantages and limitations of these ligands are discussed. In Chapter 2, studies into the metallation of ortho-substituted 1,3-bis(2-pyridylimino)isoindolate (BPI) ligands and a series of new ortho-functionalized 2,5-bis(-pyridyl)-pyrrolate (PDP) ligands are discussed. In Chapter 3, the metallation of PDP to Pt/Pd to form a series of monomer and dimer complexes is described. A rationale for monomer versus dimer formation is presented, as well as experiments into monomer/dimer interconversion. In Chapter 4, fundamental reactivity of the PDP-ligated Pt/Pd complexes toward individual steps of selective alkane functionalization is explored.


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