[PdCl(Me)(bpy)] and a mixture of the complex with cocatalysts; NaBARF (BARF = [B{C6H3(CF3)2‐3,5}4]?), NaBF4, AgBARF, AgBF4, and AgOTf, catalyze the copolymerization of 2‐phenyl‐1‐methylenecyclopropane with carbon monoxide to produce a new polyketone accompanied by ring opening of the monomer. 1H and 13C{1H} NMR spectra indicate that the polymers have two isomeric repeating units in which the phenyl substituents occupy different positions. The molecular weights of the polyketones formed by the reactions with a [Pd]/[cocatalyst]/[2‐phenyl‐1‐methyleneyclopropane] ratio of 1:3:70 are in the range of Mn = 13 100–86 000. The polymer obtained by the reaction promoted by [PdCl(Me)(bpy)]/MBARF, where M = Ag or Na, shows a narrow molecular weight distribution, Mw/Mn = 1.44 and 1.59, respectively. The catalysis is effective also for the ring‐opening copolymerization of 2‐aryl‐1‐methylenecyclopropanes bearing Me and F substituents on the phenyl ring. Isotope‐labeled experiments revealed the mechanism of the polymerization, which involves a 1,2‐insertion of the monomer into the Pd–acyl bond to produce a cyclopropylmethyl palladium intermediate, and subsequent β‐alkyl elimination to give the Pd–alkyl complex.
