The first report on the preparation, polymerization and copolymerization of two organotungsten vinyl monomers, (η5-vinylcyclopentadienyl)tricarbonylmethyltungsten (IV) and (η5-cyclopentadienylmethyl acrylate)tricarbonylmethyltungsten (IX) is described. Monomer IV was prepared from a reaction between formylcyclopentadienylsodium and hexacarbonyltungsten in DMF, followed by methylation with methyl iodide to produce (η5-formylcyclopentadienyl)tricarbonylmethyltungsten (III), and subsequent conversion of the latter into IV under phase transfer conditions employing triphenylmethylphosphonium iodide, 5 N sodium hydroxide and benzene. Moreover IX was obtained by sodium borohydride reduction of III, followed by treatment of the resulting carbinol with sodium hydride and subsequent reaction with acryloyl chloride. Monomer IV homopolymerized sluggishly, and copolymerized slowly with styrene under radical initiation in benzene solution. Copolymerizations of IV with methyl methacrylate, acrylonitrile, and N-vinyl-2-pyrrolidone were also successful. Monomer IX homopolymerized and copolymerized with styrene and with methyl acrylate. A styrene copolymer of IV when treated with iBuAlCl2 and oxygen was active as a metathesis catalyst with 3-heptene.
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Acknowledgement is made to the Donors of the Petroleum Research Fund, administered by the -American Chemical Society, and to a National Science Foundation grant to the Materials Research Laboratory, University of Massachusetts, for support of this research program (M.D.R.). The support of the Office of Naval Research (Inorgmic Polymers Program) and the Army Research Office Grant DAAG 29-76-6-0182 (to C.U.P.) is gratefully acknowledged. We also wish to thank Mr. 1%‘.C raig Spink for assistance in the synthesis of monomer IV during the early stages of the program.