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The basic objectives of this program were to elucidate the fimdamental mechanisms of Pd(H)~ and Ni(LI)-catalyzed alternating copolymerizations of carbon morioxide with olefins and to develop and investigate new catalytic systems. Specifically, well-defined organometallic precursors that yield active catalyst systems were investigated to determine the catalyst resting state, details of the carbon-carbon bond coupling processes, the kinetics of chain growth, and the ,, modes of chain termination and chain Imnsfer. Proposed transient intermediates were prepared through independent low-temperature synthesis to veri~ their involvement in the catalytic cycle. ,A Extensive mechanistic investigations have been completed on the copolymerization of “ ethylene and carbon monoxide using (phenan~oline)Pd(CH3)( OEt2)%4r g-(Ar = 3,5(CFs)&j.Hs_) as the initiators; most of these resuhs have been recently published.l Similar studies have recently been completed using various substituted styrenes and carbon monoxide and this work is being prepared for publication.2 .. . A unique method i&olving bidentate ligand exchange at the metal center (without chain transfer!) has been developed for synthesis of stereoblock alternating copolymers of CO and styrenes. Mechanistic studies have established details of the exchange process and some of these results have been communicated.3 Our most recent efforts were focused on detailed mechanistic studies of ethylene-CO and ct-olefin-CO copolymerizations using a series of Pd(II) complexes employing various bidentate phosphine Iigands. The well-defined ether complexes

Final Report: Mechanistic Studies of Transitional Metal Catalyzed Alternating Copolymerization of Carbon Monoxide with Olefins, July 1, 1994 - May 31, 1998