The copper （Ⅱ）-catalyzed polymerization of 2

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6-tribromophenol was studied using different copper（Ⅱ）catalysts. Using Taft substituent constant as parameter

copper（Ⅱ） salt has catalytic activity as ∑δ*>5.5. The reactions with copper（Ⅱ） complexes isolated show that the copper （Ⅱ） complex prepared at a mole ratio of copper （Ⅱ） chloride/sodium methoxide equals 0.5 has maximum activity. Single electron transfer reaction mechanism was proposed for the copper （Ⅱ）-catalyzed polymerization through the copper （Ⅱ）-phenoxo complex intermediate.