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Publication Date

Fall 2017

Degree Type

Thesis - Campus Access Only

Degree Name

Master of Science (MS)

Department

Chemistry

Advisor

Gilles Muller

Keywords

Chiral, Chiral Solvent Sheath, Lanthanide Complex, Pfeiffer Effect, Solvent Effects, Solvent Packing

Subject Areas

Chemistry

Abstract

The goal of this research project was to gain a more thorough understanding of how the Pfeiffer effect functions at the molecular level. We also wanted to gain a better understanding of how significant of a role solvent effects, particularly chirality transfer mechanisms, play in the mitigation of the discriminatory interactions between the added chiral species (i.e. L-serine) and the [Ln(DPA)3]3- complex. The Pfeiffer effect is observed when an optically active compound such as an amino acid is introduced to a solution containing a labile racemic metal complex leading to an equilibrium shift. The “perturbation” results in an excess of one enantiomer over the other. The shift is a result of a preferential outer sphere interaction between the introduced chiral species and one enantiomeric form ( or ) of the lanthanide complex. The speculations regarding the actual mechanism of the Pfeiffer effect tend to fall short of an accurate and complete description of the mechanism; one usually attributes the effect to a singular factor such as pH, solvent polarity, or numerous other intermolecular interactions. Through the use of the lanthanide (III) complexes [Tb(DPA)3]3- and [Eu(DPA)3]3- (where DPA= 2,6-pyridinedicarboxylate) and the amino acids L-serine and L-proline, it is becoming clear that it is not so simply described. The true mechanism is far more complicated than to attribute just a singular factor. In order to better understand the mechanism, the solvent environment must first be understood in greater detail.

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