Abstract
The reaction of the 2,4,5‐trichlorophenolate anion with 2,4‐dichlorophenol to afford trichlorinated dibenzo‐p‐dioxins (T3CDDs) is investigated at the B3LYP/6‐31+G(d) and B3LYP/6‐311+G(3df,2p)//B3LYP/6‐31+G(d)+ZPVE(B3LYP/6‐31+G(d)) levels of theory. The first stage of the process corresponds to the formation of a predioxin, which can evolve through four different routes. Two of them lead directly to the products 2,3,7‐T3CDD and 1,3,8‐T3CDD, and the other two afford different predioxin‐type intermediates, which in turn can evolve through all or some of the four routes to give new predioxins or T3CDD. Consequently, the theoretical results obtained show plainly the complex chemistry implied in the formation of dioxins from chlorophenols via anionic mechanisms by disclosing all the critical structures through which the system evolves, thus allowing assessment of the viability of the different mechanistic routes and the accessible products. The statistical thermodynamics treatment at 1 atm and 298.15, 600, 900, and 1200 K indicates that at higher temperatures, the Gibbs energy barrier for the formation of the initial predioxin is clearly the rate‐determining step for the whole process, but at lower temperatures the Gibbs energy barrier for this step is similar to those for its evolution into 2,3,7‐T3CDD. This result is in contrast with previous proposals that the closure of the central ring is the rate‐limiting step. Finally, according to our results the rate constant for the formation of polychlorinated dibenzo‐p‐dioxins increases with the temperature, in agreement with the experimental observation that the conversion of trichlorophenols increases when going from 600 to 900 K in the gas phase in the absence of catalysts, and with DFT molecular dynamics results.