Catalytic and Catalytically Relevant Formation, Activation and Functionalization of Covalent Bonds by Late Transition Metal Complexes

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In this project funded by the Chemical Catalysis Program of the Chemistry Division, Professor Alan Goldman at Rutgers University is developing new catalytic reactions to add molecules together to former larger, more complex ones. The overall goal is to develop new catalysts and catalytic processes that are both synthetically useful and practical. Professor Goldman is also studying the reaction mechanisms (i.e., how the reactions work) and the factors that control the chemistry of the catalytic reactions, which will help to optimize the outcomes of the catalysis and to add to our fundamental knowledge base about chemistry. The development of new catalytic conversions may lead to new routes to products ranging from fuels to plastics to pharmaceuticals. Products from catalysis technology have been estimated to account for nearly 20% of the U.S. Gross Domestic Product (GDP), so the potential impacts of such new chemistry could be broad. Graduate and undergraduate students are receiving broad training in chemical synthesis, characterization, mechanistic study, and computational molecular design, which are important for success in any scientific problem-solving endeavor related to catalysis. Participants in the project are beginning a collaboration with the Liberty Science Center in Jersey City, NJ to co-design an interactive touch-table exhibit for visitors to "virtually synthesize" common household chemicals such as aspirin and plastics. Eventually the plan is to expand this exhibit to other science centers, and possibly to other platforms such as personal computers, tablets, or smart phones.Professor Goldman is studying fundamental oxidative addition and M-X insertion reactions of late-transition-metal catalysts and their microscopic reverse. New SiNP, PC(4-py)P, and chiral PCP pincer ligands are being synthesized, complexed to iridium metal centers and studied for olefin insertions into M-X bonds, cleavage and insertions into C-O bonds, and ortho-directed insertions into aryl C-H bonds. Catalytic C-H bond functionalization is often frustrated by the fact that potential reagents such as carbon monoxide bind strongly bind to the coordination sites typically required to activate the C-H bond. Professor Goldman is studying how Bronsted acids catalyze C-H addition to metal carbonyl complexes that do not readily add additional equivalents of carbon monoxide. This chemistry potentially is the means to develop a hydrocarbon carbonylation catalyst. Fundamental studies of insertion into M-X bonds and C-X addition/elimination reactions (particularly X = O and N) will inform the development of new and more effective catalysts of this type. This chemistry eventually could impact commodity and fine chemical synthesis technology.