New organometallic and coordination chemistry for the formation and activation of carbon-carbon bonds

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Transition metal organometallic chemistry plays a critical role in many sectors of chemical technology. Metal-mediated organic reactions provide much of the methodology used for the development and commercial production of commodity and fine chemicals, in all industries dependent on organic synthesis and catalysis - pharmaceuticals, agricultural chemicals, polymers, and structural materials. The proposed research program is interdisciplinary, combining inorganic and organic chemistry to understand and manipulate the principles governing transition metal organometallic reactivity and function. Our approach might be described as engineering on a molecular level: the rational design and implementation of new metal-mediated organic reactions, both stoichiometric and catalytic. Our program impacts fundamental chemistry and practical applications, advancing our understanding of organometallic reaction mechanisms and introducing new transformations into organic synthesis and catalysis. This program provides a unique intellectual environment for training creative and productive young scientists, with the command and confidence necessary to solve serious research problems. Four specific investigations are proposed, ranging from new catalyst design to new strategies for the controlled cleavage of strong carbon-carbon bonds. First, new geometrically-constrained coordination complexes will be created and exploited for catalysis, with the metal(s) in strained coordination geometries. The three other projects involve the creation of new reactions in which complex organic molecules are made in a highly controlled fashion. The first expands on investigation of metal-directed radical alkylation, using metal coordination to invert natural selectivities. In the second project, new metal-mediated cycloaddition reactions will be developed for the preparation of important carbocyclic and heterocyclic materials. The third project is focused on new metal-directed ring-expansion reactions, an unusual process in which the metal cleaves open a carbon-carbon bond and inserts in a new two-carbon unit.