Catalysis of radical reactions by “naked” lithium cation

ORGN 620

Kamesh Vyakaranam1, Josiah B. Barbour2, and Josef Michl, michl@eefus.colorado.edu1. (1) Department of Chemistry and Biochemistry, University of Colorado, 215 UCB, Boulder, CO 80309-0215, (2) Department of Chemistry & Biochemistry, University of Colorado, Boulder, CO 80309-0215
LiCB11Me12 and related lithium salts are soluble in benzene, 1,2-dichloromethane, and similar solvents. The poorly solvated (“naked”) lithium cations present in these solutions are potent Lewis acids and have been reported to catalyze pericyclic reactions. We now find that they also are effective catalysts for reactions in which radicals are formed, such as the decomposition of azoisobutyronitrile (AIBN), and for reactions in which radicals participate, such as radical polymerization of unactivated terminal alkenes (ethylene, propene, isobutylene, etc.). The polymerization reactions proceed at ambient pressure and temperature.
 

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