Air-Initiated Radical Polymerization of Lithium Salts of omega-(Undecamethylcarba-closo-dodecaboran-1'-yl)alk-1-enes, CH2=CH(CH2)(n-2)C(BMe)11- Li+.

We report an easy access to the salts of the LiC(BMe)11- anion, which greatly simplifies the synthesis of compounds carrying the -C(BMe)11- substituent, including the title anions. The previously recognized and puzzling spontaneous oligomerization of the solid lithium salts CH2=CH(CH2)(n-2)C(BMe)11- Li+ upon storage under ambient conditions is now shown to proceed by a radical mechanism, with the "naked" Li+ cation acting as a catalyst. The degree of polymerization is higher in solution, especially when azoisobutyronitrile (AIBN) is used as initiator (up to approximately 50). Initiation by the thermal decomposition of AIBN is also catalyzed by naked Li+, and this initiator is effective at room temperature. Di-tert-butyl peroxide and UV irradiation can also be used. The observation of Li+ catalysis agrees with a prior prediction from ab initio calculations, according to which Li+ complexation of ethylene strongly lowers the activation energy for methyl radical addition. The results bear on the current discussion of the possible sensitivity of radical clocks to their molecular environment and suggest that naked Li+ will catalyze the radical polymerization of simple terminal alkenes.