The formation and addition polymerization of two organotungsten monomers

5-vinylcyclopentadienyl) tricarbonylmethyltungsten and (η5-cyclopentadienylmethyl acrylate)tricarbonylmethyltungsten

D. W. Macomber, M. D. Rausch, T. V. Jayaraman, R. D. Priester, C. U. Pittman

Research output: Contribution to journalArticle

30 Citations (Scopus)

Abstract

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.

Original languageEnglish (US)
Pages (from-to)353-364
Number of pages12
JournalJournal of Organometallic Chemistry
Volume205
Issue number3
DOIs
StatePublished - Feb 10 1981

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Styrene
acrylates
Benzene
Polymerization
polymerization
monomers
Monomers
styrenes
Acrylonitrile
Sodium Hydroxide
Methacrylates
Sodium
Iodides
copolymerization
Copolymerization
iodides
Methylation
Methanol
Reactive Oxygen Species
sodium hydrides

Cite this

The formation and addition polymerization of two organotungsten monomers : (η5-vinylcyclopentadienyl) tricarbonylmethyltungsten and (η5-cyclopentadienylmethyl acrylate)tricarbonylmethyltungsten. / Macomber, D. W.; Rausch, M. D.; Jayaraman, T. V.; Priester, R. D.; Pittman, C. U.

In: Journal of Organometallic Chemistry, Vol. 205, No. 3, 10.02.1981, p. 353-364.

Research output: Contribution to journalArticle

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abstract = "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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