Chiraphos (2,3-diphenylphosphinobutane) serves as a 1 highly effective ligand for nickel catalyst in the cross-2 coupling polymerization reaction. Nickel(II) catalyst 3 efficiently promotes the cross-coupling polymerization of 4 2,5-differently substituted 1,4-dihalobenzene particularly 5 bearing a sterically congested substituent at the side chain 6 affording the corresponding poly(1,4-phenylene). Such a 7 highly active catalyst allowed the polymerization with 8 diverse degree of polymerization with controlled molecular 9 weight. 10

Nickel thiocyanate complex was prepared by the reaction with Chiraphos (2S,3S-diphenylphosphinobutane) following the literature method. Thus obtained nickel complex was found to be available for the polymerization reaction of 1,4-dihalobenzene and 2-halo-3-hexylthiophene leading to poly(1,4-phenylene) and poly(3-hexylthiophene-2,5-diyl). The polymerization with other ligands such as bidentate phosphine complex of DPPE and DPPP and several N-heterocyclic carbene complexes also proceeded in a similar manner, Ni(NCS)2 complex catalyzed Suzuki–Miyaura coupling and Buchwald–Hartwig amination to afford the corresponding biaryl and arylamine, respectively, were also found to proceed successfully.