Doctor of Philosophy
Flowers, Robert A.
Titanocene(III) complexes are important single-electron reductants that have been used extensively for a variety of stoichiometric as well as catalytic reactions. Owing to their intrinsic ability to alternate between the +3 and +4 oxidation states, titanocene(III) complexes are attractive reagents for designing efficient atom-economical processes.In this dissertation, a detailed mechanistic study of an atom-economical radical arylation of amino-epoxides, catalyzed by titanocene(III) chloride, to form indoline derivatives is presented. Information gleaned from our mechanistic studies, which include the role of salt additives and the turnover-limiting step, was used to further fine-tune and enhance this radical arylation process to incorporate a wider range of amino-epoxides including electron deficient epoxides, which were recalcitrant to the arylation process.Also, an in-depth understanding of the impact of solvent and of ligands attached to titanocene(III) obtained from our mechanistic studies has led to the discovery of cationic titanocene(III) complexes as viable, stable catalysts, for performing the radical arylation of amino-epoxides to form indoline products. Finally, the development and mechanistic study of a procedurally straightforward, inexpensive, and mild approach for the reduction of aldehydes, ketones, and esters to their respective alcohols via a titanocene(III) borohydride-PMHS system is presented.
Fianu, Godfred Kwesi Delali, "Titanocene(III) Complexes: Promising Reagents for the Design of Sustainable Catalytic Processes" (2018). Theses and Dissertations. 4280.