Synthesis of Functional Polyphenylenes from Substituted Hydroquinones via Nickel(0)-Catalyzed Polymerization of Their Bismesylates

This paper reports the elaboration of a novel synthetic method for the preparation of polyphenylenes. It consists of the Ni(0)-catalyzed polymerization of bis[(methylsulfonyl)oxy] derivatives (i.e., arylene bismesylates) of substituted hydroquinones. The Ni(0) catalysts used were generated in situ from NiCl 2 (PPh 3 ) 2 , Zn, Et 4 NI in THF, dioxane, or DMAc. The influence of solvent, temperature, additional ligands, and the size and electronic properties of the substituent groups of the monomers on their polymerizability was investigated. Soluble poly(p-phenylene)s and poly(m-phenylene)s can be obtained by a proper selection of their substituents. Poly(p-phenylene)s with number-average molecular weights (relative to polystyrene standards) of up to 20 030 (DP = 101) were obtained.