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 language | English (US) |
|---|---|
| Pages (from-to) | 353-364 |
| Number of pages | 12 |
| Journal | Journal of Organometallic Chemistry |
| Volume | 205 |
| Issue number | 3 |
| DOIs | |
| State | Published - Feb 10 1981 |
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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 journal › Article
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TY - JOUR
T1 - The formation and addition polymerization of two organotungsten monomers
T2 - (η5-vinylcyclopentadienyl) tricarbonylmethyltungsten and (η5-cyclopentadienylmethyl acrylate)tricarbonylmethyltungsten
AU - Macomber, D. W.
AU - Rausch, M. D.
AU - Jayaraman, T. V.
AU - Priester, R. D.
AU - Pittman, C. U.
PY - 1981/2/10
Y1 - 1981/2/10
N2 - 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.
AB - 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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U2 - 10.1016/S0022-328X(00)82437-7
DO - 10.1016/S0022-328X(00)82437-7
M3 - Article
VL - 205
SP - 353
EP - 364
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
SN - 0022-328X
IS - 3
ER -