| The twelve vertex anionic cluster, CB11H12 -, is a weakly coordinating anion that exhibits extraordinary thermal and chemical stability. It has been used extensively as a counterion for interesting cations and as a one-electron oxidant. However, our understanding of its electronic structure and reactivity is still in its infancy. In order to understand its properties better, the fifteen methylated CB11H12 - with effective C5v symmetry have been prepared by members of the Michl research group. This dissertation describes the preparation of three of these anions and the measurement of their oxidation potentials by cyclic voltammetry in liquid SO2.;The acidity of the CH in position one of CB11H12 - and some of its methylated and halogenated derivatives were investigated using Bordwell's method in DMSO. The 12-F-CB11H11 - anion was found to be less acidic than 12-I-CB11H 11-, and both anions were found to be much less acidic than CB11H12-.;In effort to develop a safer route to fluoroalkylated carborane anions, a reaction was developed in which a metal carbenoid inserts into the BH bonds of CB11H12-. A trifluoroethylated carborane anion with a polymerizable tether was synthesized, polymerized, and tested for conductivity. The measurement suggests that this anion may be a good replacement for the sulfonate groups in NafionRTM. |
