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A mechanistic interpretation of the [(1,10-phenanthroline)Pd(CH(3))(CH(3)CN)](+)[BArF](-) (1a) and [(2,2'-bipyridine)Pd(CH(3))(CH(3)CN)](+)[BArF](-) (1b) (BArF = 3,5-(CF(3))(2)-C(6)H(3)) catalyzed perfectly alternating copolymerization of styrenes with CO is reported. The copolymerization in CH(2)Cl(2) or chlorobenzene has been found to be first order in styrene and inverse first order in CO concentrations. The microscopic steps involved in the catalytic cycle have been studied via low temperature NMR techniques. Palladium alkyl chelate complex [(2,2'-bipyridine)Pd(CHArCH(2)C(O)CH(3)](+)[BArF](-) (5b sigma) and [(2,2'-bipyridine)Pd(eta(3)-CH(CH(2)C(O)CH(3))Ar)](+)[BArF](-) (5b pi), existing in equilibrium, were prepared. Treatment of 5b sigma,pi with (13)CO followed by 4-tert-butylstyrene at -78 degrees C allowed for (13)C NMR monitoring of the alternating chain growth of a series of palladium acyl carbonyl complexes. The acyl carbonyl species, representing the catalyst resting state, is in equilibrium with a palladium acyl styrene complex. The equilibrium constant, K(4), measured between [(phen)Pd(CO)(C(O)CH(3)](+)[BArF](-) (3a) and [(phen)Pd(C(O)CH(3))-(C(6)H(5)C=CH(2))](+)[BArF](-) (8a), was determined to be 2.84 +/- 2.8 x 10(-7) at -66 degrees C. The barrier to migratory insertion in 8a was determined (DeltaG(double dagger) (-66 degrees C) = 15.6 +/- 0.1 kcal mol(-1)). From the experimentally determined kinetic and thermodynamic data for the copolymerization of styrene with CO a mechanistic model has been constructed. The ability of this model to predict catalyst turnover frequency (TOF) was used as a test of its validity. A series of para-substituted styrenes, p-XC(6)H(4)CH=CH(2) (X = -OCH(3), -CH(3), -H, -Cl), were copolymerized with CO. A Hammett treatment of TOF for the series showed that electron-donating groups increase the rate of copolymerization (rho p = -0.8). The ratio of chain transfer to chain propagation was found to increase with styrene concentration and decrease with CO concentration. Polymer end group analysis showed the presence of alpha, beta-enone end groups. The reactivity of model systems, coupled with a study of the effect of added acetonitrile, support a chain transfer mechanism involving beta-hydrogen transfer to monomer from a palladium alkyl styrene intermediate.

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Conjugated polymers possessing a poly(2,5-dimethylene-2,5-dihydrofuran) backbone were prepared through postpolymerization reaction of styrenic polyketones with bromine in one-pot reactions. The modification is proposed to proceed via condensation of two repeating units to form a fully characterized polymer with a poly(2,5-dimethylenetetrahydrofuran) backbone. Subsequent bromination and elimination of HBr yield a polymer with a fully conjugated carbon backbone. The new conjugated polymers were characterized by NMR, IR, and UV-vis spectroscopies and by CV. These polymers have strong absorption in the visible region, with the absorption peaks shifted to the NIR region upon doping with acids. The ease of the synthesis of the starting polyketone and of the modifications allows large-scale preparation of those conjugated polymers.

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