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 NiCl2(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.