Living radical polymerization of acrylates mediated by 1,3-bis(2-pyridylimino)isoindolatocobalt(II) complexes: monitoring the chain growth at the metal

A new type of mediator for cobalt(II)-mediated radical polymerization is reported which is based on 1,3-bis(2-pyridylimino)isoindolate (bpi) as ancillary ligand. The modular synthesis of the bis(pyridylimino)isoindoles (bpiH) employed in this work is based on the condensation of 2-aminopyridines with phthalodinitriles. Reaction of the bpiH protio-ligands with a twofold excess of cobalt(II) acetate or cobalt(II) acetylacetonate in methanol gave Co(bpi)(OAc)], which crystallize as coordination polymers, and a series of Co(acac)(bpi)(MeOH)], which are mononuclear octahedral complexes. Upon heating the Co(acac)(bpi)(MeOH)] compounds to 100 degrees C under high vacuum, the coordinated methanol was removed to give the five-coordinate complexes Co(acac)(bpi)]. The polymerization of methyl acrylate at 60 degrees C was investigated by using one molar equivalent of the relatively short-lived radical source 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) (V-70) as initiator (monomer/catalyst/V-70: 600:1:1). The low solubility of the acetato complexes inhibits their significant activity as mediators in this reaction, whereas the acetylacetonate complexes control the radical polymerization of methyl acrylate more effectively. The radical polymerizations of the hexacoordinate complexes did not show a linear increase in number-average molecular weight (M(n)) with conversion; however, the polydispersities were relatively low (PDI=1.12-1.40). By using the pentacoordinate complexes Co(acac)(bpi)] as mediators, a linear increase in M(n) values with conversion, which were very close to the theoretical values for living systems, and very low polydispersities (PDI<1.13) were obtained. This was also achieved in the block copolymerization of methyl acrylate and n-butyl acrylate. The intermediates with the growing acrylate polymer radical ((.)PA) were identified by liquid injection field desorption/ionization mass spectrometry as following the general formula Co(acac)(4-methoxy-bpi)-(MA)(n)-R] (MA: methyl acrylate; R: C(CH(3))(CH(2)C(CH(3))(2)OCH(3))CN), a notion also confirmed by NMR end-group analysis.