Viscosity as an Experimental Tool in Studying the Mechanism of Stereoselective and Product-Selective Chemical Transformations through Frictional Impositions

2003-05-01T00:00:00Z (GMT) by Waldemar Adam Alexei V. Trofimov
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.