Phosphinoyl and thiophosphinoylcarbodithioates: synthesis, molecular structure, and application as new efficient mediators for RAFT polymerization.

New phosphinoyl and thiophosphinoylcarbodithioates were synthesized in a one-pot reaction from the corresponding phosphinochalcogenides. Compounds of this new generation of thiocarbonylthio derivatives have been fully characterized by IR as well as (1)H, (31)P, and (13)C NMR spectroscopy and by mass spectrometry. Their solid-state structures reveal that they are isostructural but crystallize in different space groups. These new compounds are highly efficient reversible chain-transfer agents for the reversible addition-fragmentation chain transfer (RAFT) polymerization of styrene (St) and n-butyl acrylate (nBA), with controlled number-average molecular weights (Mn) and narrow dispersity values (Ð<1.3). The controlled character of the polymerization was further exemplified by MALDI-TOF mass spectrometry and the synthesis of PSt-P(nBA) diblock copolymers.