Rigid Biphenyl and Tetraphenylelement Linker Scaffolds for Superior Immobilized Catalysts

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This award is funded under the American Recovery and Reinvestment Act of 2009 (Public Law 111-5). The Inorganic, Bioinorganic and Organometallic Chemistry Program supports the research of Professor Janet Bluemel of Texas A&M University to synthesize a new generation of linkers for the immobilization of catalysts on oxide supports. New 4,4'-bisphosphine biphenyl and p-tetraphosphine tetraphenyl-element linkers incorporate rigid backbones which prevent the phosphine groups and the bound complexes from bending down to the surface of the support and decomposing. These tetraphenyl-element scaffolds offer up to three metal coordination sites per surface binding site, so that optimal surface coverages are obtained. Solid-state NMR is used to measure their translational and precession-type mobility on the surface.Special attention is given to the [(biphenyl)-R2PEt]+-O-{oxide support} linkage, as this is the first time one can probe the "flexibility" of an ionic bond. The rigid phosphine linkers are incorporated into metal catalysts for olefin hydrogenation and hydrosilylation. Students will receive interdisciplinary training with both internationally and industrially collaborative efforts.