Due to its importance in chemistry and biology, mechanisms of reactions involving phosphates are of central interest. However, only recently, quantum-chemical modeling of these reactions has become possible. With the advent of DFT calculations on phosphate-containing molecules, we have, therefore, investigated theoretically the mechanism of thiol-thione isomerization of a monothiopyrophosphate, which has been for a long time a subject of controversy. The calculations indicate that the reaction proceeds via concerted intramolecular mechanisms.
Keywords: DFT calculations; Isotope effects; Thiol-thione isomerization; Thiopyrophosphates.