Living Cyclocopolymerization through Alternating Insertion of Isocyanide and Allene via Controlling the Reactivity of the Propagation Species: Detailed Mechanistic Investigation.

Living cyclocopolymerization through the alternating insertion of an isocyanide and allene into palladium-carbon bond was developed based on the controlling the reactivity of the propagation species using bidentate ligands. We revealed that the rate of the presented cyclocopolymerization was depended on the ligands of Pd-initiator. When the palladium-methyl complexes having appropriate cis-chelating ligand, such as 1,3-bis(diphenylphosphino)propane (dppp), were used as initiator, the cyclocopolymerization of bifunctional aryl isocyanides (1) that contain both isocyano and allenyl moieties polymerized to afford poly(quinolylene-2,3-methylene)s with controlled molecular weight and narrow molecular weight distributions. The resulting polymer was characterized by 1H and 13C NMR analyses, which clearly showed that the terminal moiety of the polymer formed well-defined organopalladium complex as the resting state for the polymerization, which could undergo further polymerization; not only cyclocopolymerization with 1 but also homopolymerization of simple aryl isocyanide. In the analysis of the cyclocopolymerization mechanism, we conclusively demonstrated that the insertion reaction of isocyanide is the rate-determination step in the cyclocopolymerization, which proceeds via a five-coordinate intermediate with a geometrical change. The cis-chelating ligand controls the site interchange reaction, which dominates the reactivity of propagation species.