t-Bu3P-Coordinated 2-Phenylaniline-Based Palladacycle Complex as a Precatalyst for the Suzuki Cross-coupling Polymerization of Aryl Dibromides with Aryldiboronic Acids.

t -Bu3P-Coordinated 2-phenylaniline-based palladacycle complex, [2'-(amino-kN)[1,1'-biphenyl]-2-yl-kC]chloro(tri-t-butylphosphine)palladium, as a general, highly efficient precatalyst for the Suzuki cross-coupling polymerization of aryl dibromides with aryldiboronic acids is described. Such t-Bu3P-coordinated 2-aminobiphenyl-based palladacycle complex-catalyzed Suzuki cross-coupling polymerization afforded polymers within an hour, with the yields and the molecular weights comparable to or higher than that of polymers obtained by using other palladium catalysts with much longer polymerization time. Our study provided a highly efficient catalyst system for the Suzuki cross-coupling polymerization of aryl dihalides with aryldiboronic acids. Our study also paved the road for us to investigate other monodentate ligand-coordinated palladacycle complexes including N-heterocyclic carbine-coordinated ones for cross-coupling polymerizations.