Understanding Reactive Sulfur Species through P/S Synergy.

We investigated the differential oxidative and nucleophilic chemistry of reactive sulfur and oxygen anions (SSNO - , SNO - , NO 2 - , S 4 2- , and HS - ) using the simple reducing electrophile PPh 2 Cl. In the case of SSNO - reacting with PPh 2 Cl, a complex mixture of mono and diphosphorus products is formed exclusively in the P(V) oxidation state. We found that the phosphine stoichiometry dictates selectivity for oxidation to P=S/P=O products or transformation to P 2 species. Interestingly, only chalcogen atoms are incorporated into the phosphorus products and, instead, nitrogen is released in the form of NO gas. Finally, we demonstrate that more reducing anions (S 4 2- and HS - ) also react with PPh 2 Cl with P=S bond formation as a key reaction driving force.