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- W2114607393 abstract "The oxidative coupling of 2,6-dimethylphenol by Cu(II) complexes of “polystyrene-bound DMAP” was studied. The polymer was prepared by radical copolymerization of styrene and 4-( N -methyl- N - p -vinylbenzylamino)pyridine ( 1 ). Monomer ( 1 ) was prepared as described by Tomoi et al. [7]. By purifying the monomer by column chromatography instead of distillation, however, we succeeded in raising its yield by some 20%. Catalytic experiments supported by UV and EPR experiments revealed that in the catalytically active solution an equilibrium exists between dinuclear and mononuclear Cu(II) complexes. The concentration of the catalytically most active, mononuclear species Cu(II)(ligand) 4 (OH)Cl increases on enhancing the ligand/Cu ratio and decreases on addition of an excess of copper-coordinating hydroxide ions. From this structural point of view the polymeric catalyst proved to behave just like low molar mass Cu(II)-DMAP complexes, although the mononuclear polymeric catalyst is more stable because of a polydentate effect. From the difference in reaction order in copper for unbound and polystyrene-bound DMAP catalysts, it was concluded that for the reoxidation step dimerization of Cu(I) complexes is needed, whereas mononuclear Cu(II) complexes are the most active species for the oxidation of DMP. The mentioned dimerization is promoted by the polymer chain. The specificity of the polystyrene-bound DMAP catalyst for formation of polyphenyleneoxide exceeds 95%." @default.
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- W2114607393 date "1986-11-01" @default.
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- W2114607393 title "Copper(II) complexes of “polystyrene-bound DMAP”: Synthesis, structure and catalytic activity in the oxidative coupling of 2,6-dimethylphenol" @default.
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- W2114607393 doi "https://doi.org/10.1016/0167-6989(86)90030-9" @default.
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