Computational study on the recombination reaction between benzyl and propargyl radicals

Abstract

AbstractThe kinetics and mechanisms of the recombination reaction between benzyl and propargyl radicals have been computationally investigated by using the B3LYP, CBS‐QB3, and CASPT2 quantum chemical methods, and the steady‐state unimolecular master equation analysis based on the Rice–Ramsperger–Kassel–Marcus theory. Six distinct recombination channels arising from the radicals' nonequivalent resonance structures (three for benzyl and two for propargyl) were investigated at the CASPT2/cc‐pVTZ//B3LYP/6‐311G(d,p) level, and the respective rate constants were calculated with the variational transition state theory. It was found that the reaction dominantly proceeds by the addition of the propargyl radical to the alpha(CH2) site of the benzyl radical and the additions to the ortho‐ and the para‐sites are unfavorable due to the loss of the aromaticity. The isomerization reaction pathways of the initially formed adducts to methylenecyclopenta‐fused compounds through diradical intermediates were identified. Methylene–indanyl radicals were also identified as products, which are produced by direct H‐atom elimination reactions from the diradical and methylenated indanes. The results of the master equation analyses indicated that the 1‐methylene‐2‐indanyl radical is dominantly produced at high temperature (>1500 K), but the overall rate constant is significantly smaller than the high‐pressure limit within the pressure range studied (0.001–100 atm). The reactions of the triplet biradicals via the intersystem crossing were also suggested to be important and are discussed qualitatively. Investigations on the subsequent reactions of 1‐methylene‐2‐indanyl radicals revealed that the radicals rapidly decompose to 1‐methyleneindene or naphthalene + H. The temperature‐ and pressure‐dependent rate expressions are proposed for kinetic modeling. © 2012 Wiley Periodicals, Inc. Int J Chem Kinet 44: 206–218, 2012