Professor Robert Crabtree of Yale University is supported by the Inorganic, Bioinorganic and Organometallic Chemistry program to develop selective oxidation catalysts that utilize molecular recognition to position a remote substrate for stereocontrolled oxidation. Porphyrins and terpyridines with a linker holding a triacid recognition element serve as chelating ligands to dictate substrate geometry relative to the catalytic Mn or Fe site. Target oxidation sites include C-H bonds remote from the tether that will be stereoselectively converted to alcohol products. This project includes mechanistic tests and extensions to complex substrates like dihydrocholesterol that contain multiple CH bonds. Binding the catalysts to a titanium dioxide surface provides opportunities for realizing heterogeneous catalysis with these reagents.
Development of efficient oxidation catalysts is important for both bulk and fine chemical processes. Students supported by this award will be exposed to a wide range of chemical techniques that are important in catalysis, and they will utilize both coordination chemistry knowledge and organic synthetic skills.
