Theoretical calculations of homogeneous catalysis in the gas phase: elimination kinetics of 2,2-dimethoxypropane in the presence of HCl, F3CCOOH and CH3COOH

Abstract

ABSTRACTThe mechanisms of gas-phase elimination kinetics of 2,2-dimethoxypropane in the presence of hydrogen chloride, trifluoroacetic acid and acetic acid were studied using Moller Plesset, ab initio combined method Complete Basis Set (CBS)-QB3 and various density functional theory methods with 6-311G(d,p) and 6-311++G(d,p) basis sets. The M06-2X/6-311++G(d,p) method provided reasonable agreement with the experimental enthalpy and energy of activation. Formation of 2-methoxypropene and methanol products occurs through six-membered cyclic ring transition state (TS) structure. The TS was characterised by single imaginary frequency, and confirmed through intrinsic reaction coordinate (IRC) calculations. The IRC calculations suggest the development of a van der Waal complex between the 2, 2-dimethoxy propane and the acid catalyst, leading to the TS formation. The process of decomposition in the absence of the acid catalyst requires much higher temperature with an energy of activation above 200 kJ/mol. This fact appears to be a consequence of a four-membered cyclic TS-type of mechanism in the non-catalysed reaction. Structural parameters, analyses of natural bond orbital charges and bond orders of the acid-catalysed elimination reactions in this study suggest that the polarisation of the C–O bond, in the direction Cδ+—Oδ−, is rate-determining in the TS. These reactions are non-synchronous concerted polar in nature.