Date of Award

8-2012

Degree Type

Dissertation

Degree Name

Doctor of Philosophy

Major

Chemistry

Major Professor

Shane Foister

Committee Members

Shawn R. Campagna, Craig E. Barnes, Thomas A. Zawodzinski

Abstract

Pollution due to use of fossil fuels is a growing problem in today’s world. In recent years, chemical research has been focused on catalysis as the possible means of providing economical alternatives to conventional energy sources. Enhanced capabilities in the area of chemical catalysis could play a significant role that can extend from more efficient production of low or non-carbon fuels (e.g., water-splitting, electrolysis, methane oxidation), to more efficient fuel and electrolytic cells. This dissertation describes the homogeneous as well as heterogeneous synthesis of 1,2,4-triazole complexes with transiton metals. The application of these complexes for catalysis of hydrocarbon oxidation, ORR (oxygen reduction reaction) and aziridination are described. Extensive studies into effects of ligand topology and electronics are described. Metal complexes involving 1,2,4-triazole ligands showed remarkable selectivity and activity for hydrocarbon oxidation. These observations led to further exploration of the applications of these catalysts for ORR in fuel cells. Research efforts led to the identification of carbon black immobilized 1,2,4-triazole based catalysts as a potential alternatives for current platinum based catalysts. Finally, the utility of triazole catalysts was extended to the aziridination reaction. Reaction parameter optimization studies led to the discovery of a relatively mild Ni(II)-1,2,4-triazole based catalytic system. A broad substrate scope is observed for this system making it a potent synthetic tool for organic chemists.

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