The Effects of Binding Ligand Variation on the Nickel Catalyzed Externally Initiated Polymerization of 2-Bromo-3-hexyl-5-iodothiophene

The effects of binding ligand variation on the externally initiated Ni catalyzed polymerization of P3HT were investigated using a novel methodology allowing facile screening of ligands. P3HT was synthesized with >80% initiator incorporation for both mono‐ and bidentate phosphine ligands. Variation of the initiating aryl group demonstrated vastly superior results for o‐tolyl over p‐tolyl substituents. The first example of externally initiated P3HT using a bidentate phosphine ligand is reported. A further study into the effects of regioisomerism of the initiating aryl substituent showed the remarkable sensitivity of the initiating species.