Molecular weight growth by the phenyl + cyclopentadienyl reaction: Well-skipping, ring-opening, and dissociation

Abstract

Radical-radical reactions contribute to molecular weight growth of polycyclic aromatic hydrocarbons (PAHs), but their role is not well understood. The phenyl (Ph, C6H5) + cyclopentadienyl (C5H5) reaction has not been studied but can serve as a surrogate reaction for many reactions of larger aryl-σ radicals with resonance-stabilized π-radicals. The adducts of these reactions easily lose an H atom to produce a new π-radical. Through a combination of dilute flash pyrolysis experiments, theory, and simulation, we find that for the title reaction, substantial PhC5H4 + H is formed, dominantly by a well-skipping pathway, at conditions around 30 Torr and 1400 K. This radical is thermally stable at moderate temperatures but decomposes at higher temperatures following ring opening of the 5-member ring. Products corresponding to the loss of H, C2H2, and C3H3 are observed experimentally. Calculation of the C11H9 potential energy surface affirms that these are expected decomposition products and reveals multiple possible pathways.