This project intends to develop new catalysts for organometallic reactions using the design principles of Nature's enzymes. Addition and isomerization reactions are the focus of the research, because they are atom-economical and waste-free. Bifunctional catalysts with reactivity of both a late transition metal and a group capable of proton transfer or hydrogen bonding will be studied. The coordination, hydrogen-bond donating and accepting properties of both catalytically active and inactive complexes will be studied in order to explain how they function as catalysts. The reaction mechanisms will also be modeled by computing the maps of the reaction potential energy surfaces using density functional theory.
With this award, the Organic and Macromolecular Chemistry Program is supporting the research of Professors Douglas Grotjahn and Andrew L. Cooksy of the Department of Chemistry and Biochemistry at San Diego State University. Their research efforts revolve around the development of new classes of catalysts for the addition of water, alcohols, or similar compounds to C-C double and triple bonds. A novel feature of the catalysts is that a metal and an organic group work together to enhance catalytic efficiency. Such chemistry will contribute to environmentally benign methods for chemical synthesis since the reactions produce no waste and are catalyzed. Successful development of the methodology will have an impact on synthesis in the pharmaceutical and agricultural industries.
New molecules, based on metal atoms, have been made and tested for their ability to vastly enhance the rate of specific, desirable chemical reactions. This rate enhancement is called catalysis, and the metal-based molecules are catalysts. In particular, thousandfold acceleration has been seen for reactions that transform compounds such as acetylene into useful substances such as acetaldehyde (which is itself widely used in the manufacture of plastics and other compounds). The new catalysts increase reaction rates partly by providing a framework that houses hydrogen atoms as they move from one part of the reacting molecule to another part. This allows the hydrogens to move from one end of a carbon chain to the other, and for water to be split into pieces as its atoms are incorporated into the reactant. The structures of the catalyst and reactant molecules during the reaction and the path taken by the moving atoms have been characterized by experiments, using rare isotopes of certain atoms as tracers, and by computational work. These reactions have been studied primarily with catalyst and reactant dissolved in solution, but a method of supporting the catalysts on plastics has also been developed. Two of the catalysts are now being sold by a chemical company. This work has supported the training of two postdoctoral researchers, six graduate students and five undergraduates. One graduate student won a national award from the International Precious Metals Institute for her work. Fourteen peer-reviewed articles have been published from this work, including a cover story in the journal Dalton Transactions.
