Pulse radiolysis of aqueous solutions of sodium tetraphenylborate

In previous work on the 60Co γ-radiolysis of aqueous tetraphenylborate (TPB-) solutions carried out in this laboratory, it was found that several organic products, including benzene, phenol and biphenyl, are produced with substantial yield. However, the reaction mechanism was not established. In the present study, reactions initiated by OH· radicals, N3· radicals and e-aq in aqueous TPB- solutions were studied by pulse radiolysis using a 600 keV Febetron electron accelerator. The lack of reactivity between TPB- and e-aq was demonstrated by directly monitoring the transient optical absorbance of e-aq. Concerning the reaction with OH·, two schemes were considered: (1) electron transfer from B(C6H5)4- to OH·; or (2) OH· addition to B(C6H5)4-. Comparison of observed transient absorption spectra with expectations based on the two different schemes suggests that OH· addition is the dominant reaction pathway under conditions of N2O saturation, with an experimentally determined second-order rate constant of 6.2 x 109 M-1 s-1. A mechanism based on an initial first-order self-decomposition of the OH· adduct, (C6H5)3BC6H5OH·-, with measured rate constant of 4 x 104s-1 is proposed. Kinetic modeling on the proposed mechanistic scheme gives good agreement with our experimental results. (author)