Growth of polyphenyls via ion–molecule reactions: An experimental and theoretical mechanistic study

The reactivity of biphenylium cations C12H9+ with benzene C6H6 is investigated in a joint experimental and theoretical approach. Experiments are performed by using a triple quadruple mass spectrometer equipped with an atmospheric pressure chemical ion source to generate C12H9+ via dissociative ionization of various isomers of the neutral precursor hydroxybiphenyl (C12H10O). C–C coupling reactions leading to hydrocarbon growth are observed. The most abundant ionic products are C18H15+, C18H13+, C17H12+, and C8H7+. The dependence of product ion yields on the kinetic energy of reagent ions, as well as further experiments performed using partial isotopic labelling of reagents, support the idea that the reaction proceeds via a long lived association product, presumably the covalently bound protonated terphenyl C18H15+. Its formation is found to be exothermic and barrierless and, therefore, might occur under the low pressure and temperature conditions typical of planetary atmospheres and the interstellar medium. Theoretical calculations have focussed on the channel leading to C8H7+ plus C10H8, identifying, as the most probable fragments, the phenylethen-1-ylium cation and naphthalene, thus suggesting that the pathway leading to them might be of particular interest for the synthesis of polycyclic aromatic hydrocarbons. Both experiments and theory agree in finding this channel exoergic but hampered by small barriers of 2.7 and 3.7 kcal mol−1 on the singlet potential energy surface