Ionic Organic Reactions and Their Intermediates

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Research will continue on ionic organic reactions and their intermediates with emphasis on the role of electrophilic (proto) solvation in activating onium ions, carboxonium ions and certain carbocationic systems by interaction with the available non-bonded electron pairs of the heteroatoms. Some potential oxonium and carboxonium dications will be studied such as diprotonated alcohols, diprotonated CO, diprotonated HCN and diprotonated CO2 as well as diprotonated esters. Included will be experimental superacidic investigations based on isotopic exchange studies, as well as low temperature spectroscopic investigations and theoretical studies. The protolytic (alkylative) chemistry will also be studied. The protolytic (coordinative) activation of the Friedel-Crafts reaction will be explored in reactions of alkanes, as well as highly deactivated aromatics. Halooxonium ions and mixed halo-alkyl derivatives will be also prepared and studied in chlorination reactions. Polyhalonium dications will be explored, as will be bora-cations. The search for persistent silicenium ions will be continued, including solid state 29Si NMR studies. The recently discovered derivatization of C60 and C70 fullerenes will be followed up including halogenation, alkylation, acyclation and other reactions. %%% With this award, the Organic Synthesis Program will support the research of Dr. George A. Olah at the Univeristy of Southern California. The research will explore the generation of diprotonated species formed by the interaction of a proton with the unshared electron pairs on oxygen and nitrogen atoms in stable molecular species. The chemistry of these reactive species will be studied. This will result in the development of some new unique synthetic methodology that should benefit research in biochemistry and medicine as well as in the chemical industry.