Relationship between aromatic quadrupole moments and cation-binding of aromatics and between aromatic polarizability and anion-binding of aromatics

ORGN 623

Michael Lewis, LewisM5@slu.edu and Aimee Clements, clemenaj@slu.edu. Department of Chemistry, Saint Louis University, 3501 Laclede Avenue, Saint Louis, MO 63103
Recently, computational studies in our group have demonstrated the cation-binding ability of positive quadrupole moment (Θzz) aromatics and the anion-binding ability of negative Θzz aromatics. Using quantum mechanical calculations, we will show that the aromatic Θzz value is not a predictor of cation- or anion-binding capability and that negative Θzz aromatics can bind cations and anions, as can positive Θzz aromatics. We will discuss the relationship between the aromatic quadrupole moment and the cation-binding ability of aromatics and between the aromatic polarizability and the anion-binding ability of aromatics. We will also present the results of Morokuma-Kitaura decomposition calculations aimed at determining the electrostatic contribution (Eele) and the polarization contribution (Epol) to the overall binding enthalpy of arene-cation and arene-anion complexes. The Eele will be discussed in terms of its relationship to the aromatic quadrupole moment and the Epol term will be discussed in conjunction with the aromatic polarizability.
 

Physical Organic Chemistry: Calculations, Mechanisms, Photochemistry, and High-Energy Species
8:00 AM-12:00 PM, Thursday, 30 March 2006 Georgia World Congress Center -- C303, Oral

Division of Organic Chemistry

The 231st ACS National Meeting, Atlanta, GA, March 26-30, 2006