Synthesizing conjugated polymers via catalyst-transfer polymerization (CTP) has led to unprecedented control over polymer sequence and molecular weight. Yet many challenges remain, including broadening the monomer scope and narrowing the molecular weight dispersities. Broad polymer dispersities can arise from nonliving pathways as well as slow initiation. Previously, slow initiation was observed in Nimediated CTP of phenylene monomers. Although precatalysts with faster initiation rates have been reported, the rates still do not exceed propagation. Herein a second-and third-generation of reactive ligands are described, along with a simple method for measuring initiation rates. A precatalyst with an initiation rate that exceeds propagation is now reported, however, the resulting polymer samples still exhibit broad dispersities, suggesting that slow initiation is not the most significant contributing factor in Ni-mediated phenylene polymerizations. In addition, initiation rates measured under authentic polymerization conditions revealed that both exogenous triphenylphosphine and an ortho-trifluoroethoxy substituent on the reactive ligand have a strong influence. (C) 2017 Wiley Periodicals, Inc.