Regioselective chlorine-addition reaction toward C54Cl8 and role of chlorine atoms in Stone-Wales rearrangement.

By means of density functional theory, detailed studies of regioselective chlorine-addition reactions of two C54Cl8 isomers disclose a highly competitive advantage of #540C54Cl8 in the chlorofullerene formation process. The regioselectivity of the addition pattern in #540C54Cl8 is found to be dependent on both local and general factors. Special structural relationships reveal that the pristine cage of #540C54Cl8 can transform to that of #864C56Cl10 and #913C56Cl12 through both C2 addition and Stone–Wales rearrangement. It is found that Stone–Wales rearrangement, which is believed to be a high energy barrier reaction, can be facilitated remarkably well if chlorine atoms participate in the rearrangement process. Furthermore, investigation into the electronic properties of C54 exohedral fullerenes reveal the different impacts of halogen and hydrogen atoms.