Formation of 5- and 6-methyl-1H-indene (C10H10) via the reactions of the para-tolyl radical (C6H4CH3) with allene (H2CCCH2) and methylacetylene (HCCCH3) under single collision conditions

Phys Chem Chem Phys. 2015 Apr 28;17(16):10510-9. doi: 10.1039/c4cp04288c.


The reactions of the p-tolyl radical with allene-d4 and methylacetylene-d4 as well as of the p-tolyl-d7 radical with methylacetylene-d1 and methylacetylene-d3 were carried out under single collision conditions at collision energies of 44-48 kJ mol(-1) and combined with electronic structure and statistical (RRKM) calculations. Our experimental results indicated that the reactions of p-tolyl with allene-d4 and methylacetylene-d4 proceeded via indirect reaction dynamics with laboratory angular distributions spanning about 20° in the scattering plane. As a result, the center-of-mass translational energy distribution determined a reaction exoergicity of 149 ± 28 kJ mol(-1) and exhibited a pronounced maximum at around 20 to 30 kJ mol(-1). In addition, the center-of-mass angular flux distribution T(θ) depicted a forward-backward symmetry and indicated geometric constraints upon the decomposing complex(es). Combining with calculations, these results propose that the bicyclic polycyclic aromatic hydrocarbons, 6-methyl-1H-indene (p1) and 5-methyl-1H-indene (p2), are formed under single collision conditions at fractions of at least 85% in both reaction systems. For the p-tolyl-methylacetylene system, experiments with partially deuterated reactants also reveal the formation of a third isomer p5 (1-methyl-4-(1-propynyl)benzene) at levels of 5-10%, highlighting the importance in conducting reactions with partially deuterated reactants to elucidate the underlying reaction pathways comprehensively.