Date of Graduation

8-2012

Document Type

Dissertation

Degree Name

Doctor of Philosophy in Chemistry (PhD)

Degree Level

Graduate

Department

Chemistry & Biochemistry

Advisor/Mentor

Allison, Neil T.

Committee Member

Durham, Bill

Second Committee Member

Gawley, Robert E.

Third Committee Member

McIntosh, Matthias C.

Keywords

Pure sciences; Bromosilanes; Carbenes; Ligands; Palladium catalysis; Quinone methide

Abstract

In part I, we wish to report our approaches toward transition metal complexed ortho-quinone methide analogs. ortho-Quinone Methides are a class of highly reactive compounds with a wide range of chemical and biological applications. Previously, a stable iron complexed benzannulated 5-membered ring quinone methide analog was reported by Allison and Neal27. Herein, we report our approaches to improve the reactivity of that system by removing benzannulation as well as changing the metal from iron to manganese and rhenium.

Furthermore, a methodological study on generating carbenes under mild conditions by elimination of α-halosilanes and its application towards metal complexed quinone methide analogs will be included.

In part II, we report our attempts toward steric and electronic control of palladium-catalyzed cross coupling reactions by means of 7-membered ring carbene ligands. Cycloheptatrienylidene has recently emerged as an efficient catalyst ligand for both C-C and C-N bond forming reactions.56 Our efforts will focus on fine-tuning both the electronic environment of the metal center by benzannulation of the cycloheptatrienylidene ligand and the steric environment by addition of substituents to the ligand.

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