Dialkyl Chloronium Ions

Abstract

The carborane acid H(CHB(11)Cl(11)) reacts with chloroalkanes RCl to give isolable dialkylchloronium ion salts, [R(2)Cl][CHB(11)Cl(11)], that are stable at room temperature. X-ray crystal structures have been obtained for R = CH(3) and CH(2)CH(3), revealing bent cation structures with C-Cl-C angles of 101.5 and 105.8 degrees , respectively. The dimethylchloronium ion salt loses CH(3)Cl upon heating and forms sublimable CH(3)(CHB(11)Cl(11)), providing a clean synthetic route to an extremely potent electrophilic methylating agent. IR spectra of all species have been interpreted, including the C-Cl stretch in CH(3)-ClCHB(11)Cl(10).