Theoretical investigations on the mechanism of chalcogens exchange reaction between P(V) and P(III) compounds

Two mechanistic pathways for chalcogens transfer from P(V) to P(III) compounds were explored using density functional theory calculations and for both of them the corresponding transition states were identified. The calculations showed that transfer of sulfur and selenium proceeds most likely via an X-philic attack of the phosphorus nucleophile on the chalcogen, while for the oxygen transfer reaction, a mechanism involving a three-membered cyclic transition state is equally likely.