Solvent effect on the adduct formation of methyltrioxorhenium (MTO) and pyridine: enthalpy and entropy contributions

Abstract

1 : 1 adduct formation between methyltrioxorhenium (MTO) and pyridine in different solvents (n-hexane, benzene, chloroform, ethyl acetate, dichloromethane and acetone) was studied using spectrophotometric techniques. The formation constants were determined from the absorbance change of the adduct versus pyridine concentration. The values of the formation constants vary from 114.5 to 752.5 L mol⁻¹ at T = 20 °C depending on the dielectric constant of the solvent (ε_r = 1.89–20.7). Enthalpy and entropy changes during the adduct formation reactions were determined from van't Hoff plots. The measured enthalpy change of −37.0 to −22.2 kJ mol⁻¹ depends on ε_r, which is explained by Onsager's reaction field theory. The measured entropy change ranges from −71.2 to −36.6 J K⁻¹ mol⁻¹, and the dependence on the solvent is discussed in terms of the solvation effect.