RESUMEN
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)Câ 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.
RESUMEN
Molybdenum and chromium pentacarbonyldiphenylphosphinocarbodithioate complexes have been prepared in a one-pot reaction from the corresponding metallocarbonyldiphenylphosphine. The complexes have been characterised by IR, (1)H, (31)P and (13)Câ NMR spectroscopies and by mass spectrometry. The solid-state structures of [Cr(CO)(5){PPh(2)CS(2)CH(Ph)CH(3)}] (1) and [Mo(CO)(5){PPh(2)CS(2)CH(Ph)CH(3)}] (2) are reported. Compounds 1 and 2 are isostructural and crystallise in the triclinic P1 space group. These new organometallic compounds are highly efficient reversible chain-transfer agents for reversible addition-fragmentation chain-transfer (RAFT) polymerisation of styrene (St) and n-butyl acrylate (nBA), with controlled number-average molar mass values and narrow dispersities (<1.2). The controlled character of the polymerisation was further exemplified by the synthesis of St and nBA diblock copolymers.