GAS PHASE DECOMPOSITION OF T-BUTYL METHYL ETHER CATALYZED BY DIFFERENT HYDROGEN HALIDES: A DFT STUDY

Abstract

The gas phase decomposition of t-butyl methyl ether catalyzed by hydrogen halides is studied. Four different hydrogen halides (fluorine, chlorine, bromine, and iodine) were evaluated to determine the electronic influence of the halogen in the reaction mechanism. To describe the mechanism, the ωB97XD/LANL2DZ level of theory was used. The reactivity order found was F<Cl<Br<I. Interestingly, the activation free energy estimated for the HCl model was 133.9 kJ/mol, which is in good agreement with the experimental one (134.3 kJ/mol). Furthermore, a correlation above 0.804 was noticed when the electronegativity, the hydrogen-halide distance, and the pKa of the hydrogen halides were compared to the thermodynamic parameters (activation free energy, enthalpy, and entropy). Analyzing the mechanism in depth through the intrinsic reaction coordinate, reaction force, and reaction electronic flux plots, it was observed that though the reaction occurs in a one-step concerted way. The mechanism could be divided into two events; the first one composed by a proton transfer from the halide to the oxygen and the carbon-oxygen bond cleavage, and the second one being the rate-limiting event which includes the proton transfer from the t-butyl to the halide and the double bond formation.

Keywords

• catalysis, DFT, hydrogen halide, reaction mechanism