Chemistry ETDs

Publication Date



This investigation examined aspects of a potential catalytic route for the partial oxidation of organic substrates using molecular oxygen as the oxidant. The proposed cycle begins with the insertion of molecular oxygen into a metal hydride bond to generate a metal hydroperoxide. The next step involves the transfer of an oxygen atom to an acceptor substrate to generate an oxidized species and a metal hydroxide. The starting metal hydride can then be regenerated in two viable ways, either through use of CO or H2. The experimental plan involved the syntheses and characterization of new inorganic and organometallic complexes, and it focused on PCP and related pincer ligand systems bound to Group 9 and 10 transition metal hydrides as the potential catalyst. A prominent feature of these pincer complexes is the opportunity for modification of their electronic and steric properties. The first part of the research involved the generation of pincer metal hydrides based on a neutral ligand (PNP) as compared to its anionic counterpart (PCP). Several new PNP-Rh-H complexes were prepared and their reactions with molecular oxygen were investigated. Unfortunately, the isolation of a rhodium hydroperoxide was not achieved. The investigation reveals that these Rh(I) species are unstable and decompose immediately when allowed to react with molecular oxygen. Another PNP system was investigated in order to expand options for the potential catalytic cycle. In this case, an Ozerov-type anionic PNP ligand was used to synthesize Group 10 pincer metal hydrides. Several new symmetric PNP-M-H (M = Ni, Pd, Pt) complexes were prepared and characterized. Modification of these PNP ligands was accomplished, resulting in new unsymmetric and racemic chiral ligands and metal complexes. Several of these PNP-Pd-H complexes have been shown to react with molecular oxygen to generate palladium hydroperoxides. The oxygen atom transfer ability of these complexes was investigated through reaction with several organic substrates. As yet, however, no evidence has been observed to indicate partial oxidation via oxygen atom transfer.





Document Type


Degree Name


Level of Degree


Department Name

Department of Chemistry and Chemical Biology

First Advisor

Kemp, Richard A.

First Committee Member (Chair)

Paine, Robert T.

Second Committee Member

Wang, Wei

Third Committee Member

Curro, John