Bis(formylpyrrolyl) cobalt complexes as mediators in the reversible-deactivation radical polymerization of styrene and methyl methacrylate(Article)

The combination of [Co(II){κ2N,O-NC4H3-C(H)O}2(PMe3)2] (1) and tert-butyl-α-bromoisobutyrate (tBiB-Br) is a suitable initiation system for controlling the radical polymerization of styrene, by an atom transfer radical polymerization (ATRP) mechanism, below 70 °C and of methyl methacrylate, by an organometallic mediated radical polymerization (OMRP)/catalytic chain transfer (CCT) interplay mechanism, below 50 °C. The pure ATRP nature of styrene polymerization allowed the synthesis of the polystyrene-b-poly(methyl methacrylate) block copolymer, as confirmed by GPC/SEC and DOSY NMR studies. Attempts to isolate a Co(iii) species containing a Br atom (Co(iii)-Br), supposedly a key ATRP deactivator, by reacting 1 and tBiB-Br quantitatively afforded the cationic Co(iii) complex [Co(III){κ2N,O-NC4H3-C(H)O}2(PMe3)2]Br (2). Metathetic exchange reactions of complex 2 with TlX gave rise to analogues of the type [Co(III){κ2N,O-NC4H3-C(H)O}2(PMe3)2]X (3a, X = BF4 -; 3b, X = BPh4 -), containing non-coordinating anions. In the absence of a radical initiator, complex 2 mediated the formation of polystyrene and poly(methyl methacrylate), with poor control, likely via a generation of activators by a monomer addition (GAMA) mechanism. Complexes 3a and 3b, however, have been shown to be completely inactive. Addition of 0.5 equivalents of AIBN to 2 drastically improved the molecular weight control in the polymerization of styrene, at 70 °C, through a reverse-ATRP mechanism. © 2018 The Royal Society of Chemistry and the Centre National de la Recherche Scientifique.