Novel Inorganic Ligand Architectures for Catalysis

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T. Keith Hollis, University of California-Riverside, is supported by the Inorganic, Bioinorganic and Organometallic Chemistry Program for studies of phosphametallocene catalysts. These compounds have one or two phosphacyclopentadienyl ligands coordinated to a transition metal. The phosphorus in the aromatic ring gives rise to unique isomerization pathways, including ring slip and P-inversion. These processes have stereochemical consequences and can lead to the dynamic resolution of metallocenes, chiral catalysts and oscillating catalysts. Extensions to other heterometallocene systems such as boratabenzene, pyrrolyl and arsolyl may lead to similar isomerizations and yield additional useful chiral catalysts.Chiral metallocene catalysts have been applied in several processes, including olefin polymerization, epoxide ring opening, asymmetric hydrogenation, asymmetric allylic alkylation and enantioselective isomerization of allylic alcohols. The heterometallocenes developed in this project offer new potential catalysts for many transformations of interest to pharmaceutical and fine chemical producers. Students working on this project will be trained in organometallic and organic chemistry, including parallel combinatorial chemistry, and in polymer chemistry.