Viscosity as an experimental tool in studying the mechanism of stereoselective and product-selective chemical transformations through frictional impositions.
The analysis of these stereoselective and product-selective viscosity studies in terms of the simple free-volume model demonstrates the utility of frictional effects for the elucidation of complex reaction mechanisms in molecular transformations.
Abstract
In the present Account, we examine the viscosity dependence as a function of temperature, pressure, and solvent polarity for the double inversion in the photolytic azoalkane denitrogenation, the thermal isomerization of housanes, and stereochemical memory versus Curtin-Hammett behavior in radical-cation rearrangements. The analysis of these stereoselective and product-selective viscosity studies in terms of the simple free-volume model demonstrates the utility of frictional effects for the elucidation of complex reaction mechanisms in molecular transformations.