PALLADIUM(II)-CATALYZED ALTERNATING COPOLYMERIZATION OF ALLENE WITH CARBON-MONOXIDE AND THE SYNTHESIS OF TERPOLYMER WITH ALT-ALLENE CARBON-MONOXIDE AND ALT-ETHENE CARBON-MONOXIDE BLOCKS - SYNTHETIC AND MECHANISTIC ASPECTS

The alternating copolymerization of 3,3-dimethylallene with carbon mon oxide was achieved using [Pd(PPh3)(2)(MeCN)(2)](BF4)(2) as the catalys t, The use of bidentate phosphines resulted in drastically reduced yie lds. In order to gain insight into the copolymerization mechanism, the stepwise successive insertions of 3,3-dimethylallene and carbon monox ide into palladium-carbon bonds in the complexes, Pd(PPh3)(2)(Me)(Cl), [Pd(PPh3)(2)(C(O)C6H4-Me-p)(MeCN)](BF4), and [Pd[(Dppp)(Me)(MeCN)](BF 4) (Dppp: 1,3-bis(diphenylphosphino)propane), were studied. These stud ies, in turn, led to a novel living catalytic system which was used to synthesize a terpolymer with alt-allene-carbon monoxide and alt-ethen e-carbon monoxide blocks.