Viscosity as an experimental tool in studying the mechanism of stereoselective and product-selective chemical transformations through frictional impositions.
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.
Adam
Waldemar
W
Institute of Organic Chemistry, University of Würzburg, Am Hubland, D-97074 Würzburg, Germany. wadam@chemie.uni-wuerzburg.de
Trofimov
Alexei V
AV