Polymer syntheses utilizing diazocarbonyl compounds as monomers are described. Pd-based initiators active for the C1 polymerization of diazoacetates have been developed; the presence of η3-type anionic ligand on the Pd center has been proved to be essential for the initiator to be highly active for the polymerization. Pd complexes bearing naphthoquinone or its derivatives as a ligand were effective for the initiator generation in conjunction with NaBPh4. By using a series of bis(diazocarbonyl) compounds as monomers, three-, two-, and single-component polycondensations have been newly developed, affording unprecedented polymer structures.
