Vinyl Reactivity of (η5-Vinylcyclopentadienyl)tricarbonylmethyltungsten, a Novel Organometallic Monomer

Charles U. Pittman, T. V. Jayaraman, Ralph D. Priester, Steven Spencer, Marvin D. Rausch, David Macomber

Research output: Contribution to journalArticle

17 Citations (Scopus)

Abstract

The first vinyl organometallic monomer containing tungsten, (η6-vinylcyclopentadienyl)tricarbonylmethyltungsten (4), was homopolymerized and copolymerized with styrene, acrylonitrile, methyl methacrylate, and N-vinyl-2-pyrrolidone, using azobis(isobutyronitrile) (AIBN) as the initiator. Reactivity ratios for the styrene (M2) copolymerization of 4, initiated by AIBN in benzene solutions, were = 0.16 and r2 = 1.55 from which the Alfrey-Price parameters e = -1.98 and Q = 1.66 were calculated. Thus, (η5-vinylcyclopentadienyl)tricarbonylmethyltungsten is an exceptionally electron-rich vinyl monomer, closely resembling vinylferrocene, (η5-vinylcyclopentadienyl)tricarbonylmanganese, and (η5-vinylcyclopentadienyl) dicarbonylnitrosylchromium in this respect. This is the first vinyl monomer known to have an M-CH3 (M is a transition metal) bond. Styrene polymerizations in the presence of (η5-cyclopentadienyl)- tricarbonylmethyltungsten were carried out to evaluate the possibility that the methyl group is a good hydrogen atom donor (thereby serving as an inhibitor or a chain transfer agent). No evidence was obtained for significant chain transfer activity. Similarly, neither (η5-cyclopentadienyl)tricarbonylmanganese nor poly(η6-vinylcyclopentadienylRricarbonylmanganese acted as efficient chain transfer agents in styrene polymerizations.

Original languageEnglish (US)
Pages (from-to)237-241
Number of pages5
JournalMacromolecules
Volume14
Issue number2
DOIs
StatePublished - Jan 1 1981

Fingerprint

Styrene
Organometallics
Monomers
Polymerization
Acrylonitrile
Tungsten
Methacrylates
Benzene
Copolymerization
Transition metals
Hydrogen
Atoms
Electrons
azobis(isobutyronitrile)

Cite this

Vinyl Reactivity of (η5-Vinylcyclopentadienyl)tricarbonylmethyltungsten, a Novel Organometallic Monomer. / Pittman, Charles U.; Jayaraman, T. V.; Priester, Ralph D.; Spencer, Steven; Rausch, Marvin D.; Macomber, David.

In: Macromolecules, Vol. 14, No. 2, 01.01.1981, p. 237-241.

Research output: Contribution to journalArticle

Pittman, Charles U. ; Jayaraman, T. V. ; Priester, Ralph D. ; Spencer, Steven ; Rausch, Marvin D. ; Macomber, David. / Vinyl Reactivity of (η5-Vinylcyclopentadienyl)tricarbonylmethyltungsten, a Novel Organometallic Monomer. In: Macromolecules. 1981 ; Vol. 14, No. 2. pp. 237-241.
@article{24e0f598e74b4611b804f3ca3e6d2adb,
title = "Vinyl Reactivity of (η5-Vinylcyclopentadienyl)tricarbonylmethyltungsten, a Novel Organometallic Monomer",
abstract = "The first vinyl organometallic monomer containing tungsten, (η6-vinylcyclopentadienyl)tricarbonylmethyltungsten (4), was homopolymerized and copolymerized with styrene, acrylonitrile, methyl methacrylate, and N-vinyl-2-pyrrolidone, using azobis(isobutyronitrile) (AIBN) as the initiator. Reactivity ratios for the styrene (M2) copolymerization of 4, initiated by AIBN in benzene solutions, were = 0.16 and r2 = 1.55 from which the Alfrey-Price parameters e = -1.98 and Q = 1.66 were calculated. Thus, (η5-vinylcyclopentadienyl)tricarbonylmethyltungsten is an exceptionally electron-rich vinyl monomer, closely resembling vinylferrocene, (η5-vinylcyclopentadienyl)tricarbonylmanganese, and (η5-vinylcyclopentadienyl) dicarbonylnitrosylchromium in this respect. This is the first vinyl monomer known to have an M-CH3 (M is a transition metal) bond. Styrene polymerizations in the presence of (η5-cyclopentadienyl)- tricarbonylmethyltungsten were carried out to evaluate the possibility that the methyl group is a good hydrogen atom donor (thereby serving as an inhibitor or a chain transfer agent). No evidence was obtained for significant chain transfer activity. Similarly, neither (η5-cyclopentadienyl)tricarbonylmanganese nor poly(η6-vinylcyclopentadienylRricarbonylmanganese acted as efficient chain transfer agents in styrene polymerizations.",
author = "Pittman, {Charles U.} and Jayaraman, {T. V.} and Priester, {Ralph D.} and Steven Spencer and Rausch, {Marvin D.} and David Macomber",
year = "1981",
month = "1",
day = "1",
doi = "10.1021/ma50003a002",
language = "English (US)",
volume = "14",
pages = "237--241",
journal = "Macromolecules",
issn = "0024-9297",
publisher = "American Chemical Society",
number = "2",

}

TY - JOUR

T1 - Vinyl Reactivity of (η5-Vinylcyclopentadienyl)tricarbonylmethyltungsten, a Novel Organometallic Monomer

AU - Pittman, Charles U.

AU - Jayaraman, T. V.

AU - Priester, Ralph D.

AU - Spencer, Steven

AU - Rausch, Marvin D.

AU - Macomber, David

PY - 1981/1/1

Y1 - 1981/1/1

N2 - The first vinyl organometallic monomer containing tungsten, (η6-vinylcyclopentadienyl)tricarbonylmethyltungsten (4), was homopolymerized and copolymerized with styrene, acrylonitrile, methyl methacrylate, and N-vinyl-2-pyrrolidone, using azobis(isobutyronitrile) (AIBN) as the initiator. Reactivity ratios for the styrene (M2) copolymerization of 4, initiated by AIBN in benzene solutions, were = 0.16 and r2 = 1.55 from which the Alfrey-Price parameters e = -1.98 and Q = 1.66 were calculated. Thus, (η5-vinylcyclopentadienyl)tricarbonylmethyltungsten is an exceptionally electron-rich vinyl monomer, closely resembling vinylferrocene, (η5-vinylcyclopentadienyl)tricarbonylmanganese, and (η5-vinylcyclopentadienyl) dicarbonylnitrosylchromium in this respect. This is the first vinyl monomer known to have an M-CH3 (M is a transition metal) bond. Styrene polymerizations in the presence of (η5-cyclopentadienyl)- tricarbonylmethyltungsten were carried out to evaluate the possibility that the methyl group is a good hydrogen atom donor (thereby serving as an inhibitor or a chain transfer agent). No evidence was obtained for significant chain transfer activity. Similarly, neither (η5-cyclopentadienyl)tricarbonylmanganese nor poly(η6-vinylcyclopentadienylRricarbonylmanganese acted as efficient chain transfer agents in styrene polymerizations.

AB - The first vinyl organometallic monomer containing tungsten, (η6-vinylcyclopentadienyl)tricarbonylmethyltungsten (4), was homopolymerized and copolymerized with styrene, acrylonitrile, methyl methacrylate, and N-vinyl-2-pyrrolidone, using azobis(isobutyronitrile) (AIBN) as the initiator. Reactivity ratios for the styrene (M2) copolymerization of 4, initiated by AIBN in benzene solutions, were = 0.16 and r2 = 1.55 from which the Alfrey-Price parameters e = -1.98 and Q = 1.66 were calculated. Thus, (η5-vinylcyclopentadienyl)tricarbonylmethyltungsten is an exceptionally electron-rich vinyl monomer, closely resembling vinylferrocene, (η5-vinylcyclopentadienyl)tricarbonylmanganese, and (η5-vinylcyclopentadienyl) dicarbonylnitrosylchromium in this respect. This is the first vinyl monomer known to have an M-CH3 (M is a transition metal) bond. Styrene polymerizations in the presence of (η5-cyclopentadienyl)- tricarbonylmethyltungsten were carried out to evaluate the possibility that the methyl group is a good hydrogen atom donor (thereby serving as an inhibitor or a chain transfer agent). No evidence was obtained for significant chain transfer activity. Similarly, neither (η5-cyclopentadienyl)tricarbonylmanganese nor poly(η6-vinylcyclopentadienylRricarbonylmanganese acted as efficient chain transfer agents in styrene polymerizations.

UR - http://www.scopus.com/inward/record.url?scp=0013264339&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0013264339&partnerID=8YFLogxK

U2 - 10.1021/ma50003a002

DO - 10.1021/ma50003a002

M3 - Article

AN - SCOPUS:0013264339

VL - 14

SP - 237

EP - 241

JO - Macromolecules

JF - Macromolecules

SN - 0024-9297

IS - 2

ER -