The goal of this project is to discover cases of enantioselectivity in atom-transfer redox reactions of transition metal complexes. A chiral metal complex oxidant, such as delta [Co(edta)C1]2-, will be allowed to react with a labile racemic reductant, such as [Cr(en)2(OH2)2]2+, and the product will be analyzed for enantiomeric excess by circular dichroism and uv-visible spectrophotometry. The value of the enantiomeric excess will be used to determine the relative rates of reaction of the chiral oxidant with the delta and delta forms of the reductant. Experiments are also planned using chiral reductants and racemic oxidants. The chiral metal complexes will be prepared by known methods. The discovery of enantioselectivity in the atomi-transfer reaction should lead to a better understanding of the rates of inner-sphere redox reactions, and of the steric factors influencing enantioselectivity. The potential long-term applications of this information include new chiral synthetic redox reagents for pharmaceutical and natural product syntheses and new electroanalytical methods for bioanalytes.
