Dr. Ian P. Rothwell, Department of Chemistry, Purdue University, is supported by the Inorganic, Bioinorganic, and Organometallic Chemistry Program of the Chemistry Division, for research into early transition metal aryloxide chemistry. The central theme of the project involves the use of sterically bulky aryloxide ligation to support both stiochiometeric and catalytic reactivity of unsaturated small molecules at transition metal centers. Studies will aim toward a mechanistic understanding of titanium-aryloxide catalyzed [2+2+1] acetylene trimerization and the development of the synthetic utility of the reaction. New C2 symmetric, chiral aryloxides will be used as monodentate supporting ligands to carry out asymmetric carbon-carbon bond forming reactions. Fundamental studies of the factors controlling both kinetic and thermodynamic resolution of the chiral species will be carried out. Finally, cationic metallacyclic niobium and tantalum complexes will be prepared.
Sterically bulky groups bound to transition metals are often effective in preventing reactants of certain size and shape from accessing the metal center. As a consequence, the reactions that do occur produce products with a preferred geometry. In this study, bulky alkoxide groups will be used to effect stereospecific reactivity to some early transition metal promoted reactions of utility in the synthesis of organic compounds.
