On the Synthesis and Reactivity of Potassium Phosphinophosphido Dithioformates

The synthesis of sterically demanding 2,6‐bis(2,4,6‐trimethylphenyl)phenyl (Ter)‐stabilized potassium phosphinophosphido dithioformates 1a–b K[TerP(CS 2 )PR 2 ] via conversion of the corresponding potassium phosphinophosphides K[TerP–PR 2 ] (R = i Pr, t Bu) with CS 2 is reported. In solution, the dithioformates 1a–b undergo a migration reaction, resulting in the formation of anionic phosphanylthioketones, K[TerPC(=S)–P(S)R 2 ] ( 2a‐b ), bearing phosphanylthiolate groups. The cocrystallization of compounds 1a and 2a allows simultaneous structural characterization of both, and the crystallization of 2a from THF or benzene affords specific solvates with solvent‐dependent discrete dimers or polymeric chains, respectively.