Knowledge Bank

It will be demonstrated that microwave spectroscopic relative intensity measurements provide a ready means of studying the kinetics of relatively slow unimolecular isomerizations, rearrangements, or dissociations. The method requires only a minimum of care when applied to isomerizations, $A\leftrightarrow B$ in which A and B are essentially the same molecular species. The particular case to be demonstrated will be the ring inversion isomerization of exo-2,3-dideuterobicyclo[2.1.0]pentane to endo-2,3-dideuterobicyclo[2.1.0]pentane. Results and analysis to be presented lead to the following Arrhenius expression: $$ k = 1.52 \times 10^{14} \exp(-37.7 kcal / RT) sec^{-1}."" $$