Rigid Chelating Ligands as Tools for Discovery of New Reactions and Applications in Catalysis

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This research award in the Inorganic, Bioinorganic and Organometallic program supports work by Professor Oleg Ozerov at Brandeis University to explore the chemistry of transition metal complexes supported by a series of rigid pincer-type ligands. The modular construction and the rigidity will allow for logical and systematic variation of the electronic interactions of the supporting ligands with the transition metal centers. New catalytic transformations by the designed metal complexes will be targeted, such as boron-boron bond formation and rhodium-catalyzed carbon-carbon and carbon-heteroatom coupling reactions. The pursuit of catalytic applications will take place in synergy with fundamental explorations: generation of a unified scale for reactions of simple and oxidative addition, possible observation of a transition metal methane complex and of a gold hydride complex, and studies of electronic consequences of severe unsaturation at the metal center. Research results will be used to create educational materials, which will be disseminated. An integral part of the work is the collaboration with colleagues at other, especially primarily undergraduate, institutions. Prof. Anthony Fernandez of Merrimack College will be supported through a subaward to investigate solid-state oxidative addition reactions. A regional undergraduate research symposium will be organized to promote undergraduate research and enhance ties in the regional chemistry community. Transition metal catalysis is indispensable in many industrial processes of importance to modern society. Chelating supporting ligands can be used to stabilize homogeneous transition metal catalysts. Using a series of modularly variable, rigidly constructed ligands will permit the development of better understanding of the influence of the individual donor sites on the overall reactivity of the metal complex.