Off-campus UMass Amherst users: To download dissertations, please use the following link to log into our proxy server with your UMass Amherst user name and password.
Non-UMass Amherst users, please click the view more button below to purchase a copy of this dissertation from Proquest.
(Some titles may also be available free of charge in our Open Access Dissertation Collection, so please check there first.)
Methodology and mechanism: Reinvestigating the Ullmann reaction
We have combined the tools of organometallic chemistry with those of organic chemistry, and explored methodology and mechanism of palladium and copper-based catalysis. Organometallic chemistry plays a prominent role in industrial and academic laboratories, and developments in this field continue to expand our fundamental understating of chemical reactions. Herein, we report on a specific failure of a palladium-catalyzed coupling reaction, and the subsequent development of alternative copper-based methodologies. We have developed a new cross coupling protocol for the synthesis of unsymmetrical triarylphosphines, using copper-based catalysis. Furthermore, we conducted a thorough investigation into the mechanism of the centuryold Ullmann coupling. Our mechanistic research is based on rational experimental design intended to address fundamental questions regarding copper-based catalysis. One such question is: what is the nature of the reaction intermediate( s); our data is inconsistent with copper(III) intermediates. ^
Derek Van Allen,
"Methodology and mechanism: Reinvestigating the Ullmann reaction"
(January 1, 2004).
Electronic Doctoral Dissertations for UMass Amherst.