Mechanistic studies of the copolymerization of olefins and carbon monoxide by bidentate phosphine Pd(II) catalysts

Chapter One summarizes the previous work done in the preparation of copolymers of ethylene and carbon monoxide. Special emphasis is given to background information on the transition metal-catalyzed alternating copolymerization of ethylene and carbon monoxide. The copolymerization is thought to proceed by perfectly alternating migratory insertion reactions of intermediate olefin acyl and alkyl carbonyl complexes. The majority of the catalytic systems are ill-defined and very few reports exist of the reactive intermediates involved in the copolymerization.;Chapter II describes the characterization of a series of bidentate phosphine Pd(II) complexes relating to the migratory insertion steps involved in the copolymerization of ethylene and CO. The direct observation of alkyl olefin and alkyl carbonyl complexes have allowed for study of these migratory insertion rates for a variety of bidentate phosphine Pd(II) complexes. The effect of the bite angle of P-Pd-P has been compared to the role of sterics in the migratory insertion reactions and catalytic dimerization of ethyiene.;Chapter III reports the studies concerning the resting state of copolymerization of ethylene and CO by the (dppp)Pd(Me)(OEt;Chapter IV describes the copolymerization of olefins and CO by well-defined catalyst systems in aprotic solvents. The relative rates of copolymerization of ethylene and CO using variety of bidentate phosphine Pd(II) catalysts systems has been reported. High molecular weight polymers with relatively low molecular weight distributions have been isolated. Catalyst lifetimes of the DPPP and DPPB catalyst systems has been qualitatively studied. A qualitative experiment concerning the pressure effects of CO on the copolymerization of CO and 1-hexene using the DPPP catalyst system has also been described.