Stone-Wales Rearrangements in Hydrocarbons: From Planar to Bowl-Shaped Substrates.

Carbene, cyclobutyl, and potential diradical mechanisms were studied computationally for Stone-Wales rearrangements in several derivatives of as-indacene and pyracyclene, including cyclopent[hi]acephenanthrylene, dicyclopenta[cd,fg]pyrene, corannulene, diindeno[1,2,3,4-defg;1',2',3',4'-mnop]chrysene, and semibuckminsterfullerene. At the UM06-2X/cc-pVDZ and BD(T)/cc-pVDZ//UM06-2X/cc-pVDZ levels of theory, free energies of reaction reveal that transformations involving an increase in curvature are thermodynamically unfavorable. In addition, the carbene transition states or intermediates (corrected to 1000 °C) are generally around 100-120 kcal/mol higher than starting substrates, except for as-indacene (80 kcal/mol), which is the only process considered here that is predicted to have a barrier accessible under typical flash vacuum pyrolysis conditions.

Stone-Wales rearrangements in polycyclic aromatic hydrocarbons: a computational study.

Mechanisms for Stone-Wales rearrangements (SWRs) in polycyclic unsaturated hydrocarbons containing a pentafulvalene core have been studied using density functional, coupled cluster, and multiconfigurational methods. At the BD(T)/cc-pVDZ//(U)M06-2X/cc-pVDZ level of theory, free energies of activation (at 1000 °C) range from ca. 70 kcal/mol for the model system pentafulvalene → naphthalene (1 → 2) to >110 kcal/mol for the degenerate SWR of pyracyclene (3).