Hydrogen atom mediated Stone-Wales rearrangement of pyracyclene: a model for annealing in fullerene formation

We have investigated the Stone-Wales (SW) rearrangement of pyracyclene (C(14)H(12)) using quantum mechanical molecular modeling. Of particular interest in this study is the effect of an added hydrogen atom on the barriers to SW rearrangement. Hydrogen atoms are found in high abundance during combustion, and their effect upon isomerization of aromatic compounds to more stable species may play an important role in the combustion synthesis of fullerenes. We have calculated the barriers for the SW rearrangement in pyracyclene using density functional theory B3LYP/6-31G(d) and B3LYP/6-311G(d,p). Two mechanisms have been investigated: (i) a mechanism with two identical transition states of C(1) symmetry and a cyclobutyl intermediate and (ii) a mechanism with one transition state containing an sp(3) carbon (J. Am. Chem. Soc. 2003, 125, 5572-5580; Nature 1993, 366, 665-667). We find that the barriers for these mechanisms are 120.0 kcal mol(-1) for the cyclobutyl mechanism and 130.1 kcal mol(-1) for the sp(3) mechanism. Adding a hydrogen atom to the internal bridge carbon atoms of pyracyclene reduces the barrier of the cyclobutyl mechanisms to 67.0 kcal mol(-1) and the sp(3) mechanism to 73.1 kcal mol(-1). The bonding of carbon atoms in pyracyclene is similar to those found in isomers of C(60), and the barriers are low enough so that these reactions can become significant during fullerene synthesis in flames. Adding hydrogen atoms to the external bridge atoms on pyracyclene produces a smaller reduction in the SW barrier and adding hydrogen atoms to nonbridge external carbon atoms results in no reduction of the barrier.