ORGN 102 |
| Many of the reported experimental examples of anion-π interactions involving aromatics have the arene ring bound to a transition metal. Herein, we will report on a computational study into the preference of anions to bind to the π-face of metal bound aromatics or to the metal. We investigated arene-transition metal complexes with the general formula Ar–TM2+–Cp, where Ar is a substituted aromatic ring, TM2+ is either Fe2+ or Ru2+, and Cp is cyclopentadienyl anion. We have calculated the binding of Br–, Cl– and F– to both the face of the substituted benzene ring and to the metal center. All binding energies were determined at the MP2(full)/6-311++G**//B3LYP/6-311++G** level of theory. We will discuss the effect of benzene ring substitution on the preference of the anion to bind either to the π-face of the aromatic or to the metal center. Specifically, we will report on what physical properties of the substituted aromatics can be used to discern whether an anion will bind to the metal or to the face of the aromatic. We will also present our results in the context of experimental crystallographic data. |
|
Physical Organic Chemistry, Combinatorial and Process Chemistry, New Reactions and Methodology, Peptides, Proteins and Amino Acids
8:00 PM-10:00 PM, Sunday, April 6, 2008 Morial Convention Center -- Hall A, Poster
Division of Organic Chemistry |