Unsupported Z-ligands as key Initiators of New Catalytic Processes

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With the support of the Chemical Structure, Dynamics, and Mechanisms B (CSDM-B) and Chemical Catalysis Programs in the Division of Chemistry, Professor Michel R. Gagné of the University of North Carolina at Chapel Hill is studying the fundamental structure of ligands that coordinate to metal complexes. The goal of changing the properties of metal-ligand bonds will enable new catalytic reactions to be discovered. Catalysis is a cornerstone technology that underpins all industrial chemical transformations and is therefore of enormous global economic impact. The Gagné project could potentially uncover entirely new ways for ligands to behave, which would consequently enable new catalytic reactions and have impact across the field of organometallic chemistry in both academia and industry. One focus area will be on activating C–O bonds; these are ubiquitous in biorenewable sources of carbon.The Gagné group will study the fundamental reactivity of unsupported ligands whose reactivity, but also perhaps whose structure can be described as Z-like. The Z-designation for a ligand is not common and is reserved for those ligands that act as electrophiles. The addition of a nucleophile to such a ligand cleaves the M-Z bond in a manner that reduces the metal and will enable additional downstream chemistry. The specific focus will be on metal-silicon complexes that act as sources of silylium, Si+ ions (and reduced metal), along with metal-iodide complexes that act as sources of iodonium (I+) ions and reduced metal. The role of metal oxidation state and supporting ligands on the structure and reactivity of the putative Z ligand are of paramount interest.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.