This award in the Division of Chemistry supports research by Professor Melanie Sanford at the University of Michigan to investigate the mechanism, scope, selectivity, and ligand effects in stoichiometric reactions involving Pd(III) and Pd(IV) intermediates. The reactivity and selectivity profiles discovered will enable the rational design of new catalytic transformations. Palladium is an extremely important transition metal that is widely used in homogeneous catalytic transformations for the construction of carbon-carbon and carbon-heteroatom bonds. These reactions have found extensive application in the synthesis of pharmaceuticals, natural products, fine chemicals, and commodity chemicals. The proposed research will demonstrate the feasibility of diverse organometallic reactions (including C-H activation, migratory insertion, and nucleopalladation) at appropriately designed high oxidation state palladium complexes. Ultimately, the novel reactivity and selectivity profiles established herein will enable the rational design of new catalytic transformations.
The PI and coworkers will expand an outreach program for high school students called "Science Saturdays", which promotes broader participation in the physical sciences by exposing students to an authentic research-like experience, to another site in Michigan. This laboratory trains a diverse set of students (29 total PhD students and post-docs since 2003), of whom 17 are women and 3 are members of underrepresented minority groups. Graduate and undergraduate students working on this project will receive interdisciplinary training in inorganic synthesis, inorganic reaction mechanisms, and synthetic organic chemistry.
Palladium is an extremely important transition metal that is widely used in catalytic reactions for the construction of carbon–carbon and carbon–heteroatom bonds. These reactions have found extensive application in the synthesis of pharmaceuticals, natural products, fine chemicals, and commodity chemicals. In fact, the 2010 Nobel Prize in Chemistry was awarded for advances in palladium catalysis. The current project has advanced new knowledge in the field of palladium chemistry, specifically the chemistry of palladium in the highly unusual 4+ oxidation state [Pd(IV)]. The project has primarily focused on studying the mechanisms of two fundamental reactions: reductive elimination and C-H activation at Pd(IV). Key outcomes of these studies include: (1) establishing new reductive elimination reactions from Pd(IV) and (2) establishing the feasibility and mechanism of CH activation at Pd(IV). These results have been disclosed to the public in 11 peer reviewed publications in top chemistry journals, including Nature, the Journal of the American Chemical Society , Chemical Science, and Organometallics. The concepts gleaned from these studies have the potential to positively impact the development of more efficient and sustainable routes to important chemicals and pharmaceuticals. In addition, this project has trained a diverse set of graduate students and post-doctoral scholars. Furthermore, the PI has served as faculty director for the UM FEMMES (Females Excelling More in Engineering and Science) Chapter, which exposes middle school girls to experiments and career opportunities in science.
