Ring‐Opening Copolymerization of 2‐Aryl‐1‐methylenecyclopropanes with Carbon Monoxide Initiated by Pd–bpy Complexes

[PdCl(Me)(bpy)] and a mixture of the complex with cocatalysts; NaBARF (BARF = [B{C 6 H 3 (CF 3 ) 2 ‐3,5} 4 ] − ), NaBF 4 , AgBARF, AgBF 4 , 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. 1 H and 13 C{ 1 H} 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 M n  = 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, M w / M n  = 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.