Diverse stereocontrol effects induced by weakly coordinating anions. Stereospecific olefin polymerization pathways at archetypal Cs- and C1-symmetric metallocenium catalysts using mono- and polynuclear halo-perfluoroarylmetalates as cocatalysts

John Roberts, Ming Chou Chen, Afif M. Seyam, Ting Li, Cristiano Zuccaccia, Nicholas G. Stahl, Tobin J Marks

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Abstract

Counteranion effects on propylene polymerization rates and stereoselectivities are compared using Cs-symmetric Me 2C(Cp)(Flu)ZrMe2 (1; Cp = C5H 45-cyclopentadienyl; Flu = C13H 8, η5-fluorenyl) and C1-symmetric Me 2Si(OHF)(CpR*)ZrMe2 (2; OHF = C13H 16, η5-octahydrofluorenyl; CpR* = η5-3-(-)-menthylcyclopentadienyl) precatalysts activated with the mononuclear and polynuclear perfluoroarylborate, -aluminate, and -gallate cocatalysts/activators B(C6F5)3 (3), B(o-C 6F5C6F4)3 (4), AI(C 6F5)3 (5), Ph3C+B(C 6F5)4- (6) Ph3C +FAI(o-C6F5C6F4) 3- (7), Ga(C6F5)3 (8), and recently reported mono- and polymetallic trityl perfluoroarylhalometalates Ph3C+FB(C6F5)3 - (9), Ph3C+FB(o-C6F 5C6F4)3- (10), (Ph 3C-)xF x[AI(C6F 5)3]yx- (x = 1, y = 1, 11; X = 1, y = 2, 12; x = 2, y = 3, 13), Ph3C+(C6F 5)3AIFAI(o-C6F5C6F 4)3- (14), Ph3C +XAI(C6F5)3- (X = Cl, 15; X = Br, 16), and Ph3C+F[Ga(C6F 5)3]2- (17). Temperature, propylene concentration, and solvent polarity dependence are surveyed in polymerizations catalyzed by 1 activated with cocatalysts 3-16 and with a 1:2 ratio of Ph 3CCI and 5, and with a 1:2 ratio of Ph3CBr and 5, and by 2 activated with 3, 6, 7, 12, and 14. Remarkable stereocontrol with high activities is observed for 1 + 12 and 1 + 14. Polypropylene samples produced using C1-symmetric precatalyst 2 are subjected to microstructural analyses using stochastic models describing the relative contributions of enantiofacial misinsertion and backskip processes. A powerful technique is introduced for calculating interparametric correlation matrices for these nonlinear stochastic models. The collected results significantly extend what is known about ion-pairing effects in the case of Cs-symmetric precatalyst 1 and allow these findings to be applied to the case of C 1-symmetric precatalyst 2 as an agent of isospecific propylene polymerization.

Original languageEnglish
Pages (from-to)12713-12733
Number of pages21
JournalJournal of the American Chemical Society
Volume129
Issue number42
DOIs
Publication statusPublished - Oct 24 2007

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Alkenes
Polymerization
Olefins
Propylene
Anions
Negative ions
Stochastic models
Catalysts
Stereoselectivity
Nonlinear Dynamics
Polypropylenes
Ions
Temperature
propylene

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

@article{e303edc70d0a408cb375caaef1e483d3,
title = "Diverse stereocontrol effects induced by weakly coordinating anions. Stereospecific olefin polymerization pathways at archetypal Cs- and C1-symmetric metallocenium catalysts using mono- and polynuclear halo-perfluoroarylmetalates as cocatalysts",
abstract = "Counteranion effects on propylene polymerization rates and stereoselectivities are compared using Cs-symmetric Me 2C(Cp)(Flu)ZrMe2 (1; Cp = C5H 4,η5-cyclopentadienyl; Flu = C13H 8, η5-fluorenyl) and C1-symmetric Me 2Si(OHF)(CpR*)ZrMe2 (2; OHF = C13H 16, η5-octahydrofluorenyl; CpR* = η5-3-(-)-menthylcyclopentadienyl) precatalysts activated with the mononuclear and polynuclear perfluoroarylborate, -aluminate, and -gallate cocatalysts/activators B(C6F5)3 (3), B(o-C 6F5C6F4)3 (4), AI(C 6F5)3 (5), Ph3C+B(C 6F5)4- (6) Ph3C +FAI(o-C6F5C6F4) 3- (7), Ga(C6F5)3 (8), and recently reported mono- and polymetallic trityl perfluoroarylhalometalates Ph3C+FB(C6F5)3 - (9), Ph3C+FB(o-C6F 5C6F4)3- (10), (Ph 3C-)xF x[AI(C6F 5)3]yx- (x = 1, y = 1, 11; X = 1, y = 2, 12; x = 2, y = 3, 13), Ph3C+(C6F 5)3AIFAI(o-C6F5C6F 4)3- (14), Ph3C +XAI(C6F5)3- (X = Cl, 15; X = Br, 16), and Ph3C+F[Ga(C6F 5)3]2- (17). Temperature, propylene concentration, and solvent polarity dependence are surveyed in polymerizations catalyzed by 1 activated with cocatalysts 3-16 and with a 1:2 ratio of Ph 3CCI and 5, and with a 1:2 ratio of Ph3CBr and 5, and by 2 activated with 3, 6, 7, 12, and 14. Remarkable stereocontrol with high activities is observed for 1 + 12 and 1 + 14. Polypropylene samples produced using C1-symmetric precatalyst 2 are subjected to microstructural analyses using stochastic models describing the relative contributions of enantiofacial misinsertion and backskip processes. A powerful technique is introduced for calculating interparametric correlation matrices for these nonlinear stochastic models. The collected results significantly extend what is known about ion-pairing effects in the case of Cs-symmetric precatalyst 1 and allow these findings to be applied to the case of C 1-symmetric precatalyst 2 as an agent of isospecific propylene polymerization.",
author = "John Roberts and Chen, {Ming Chou} and Seyam, {Afif M.} and Ting Li and Cristiano Zuccaccia and Stahl, {Nicholas G.} and Marks, {Tobin J}",
year = "2007",
month = "10",
day = "24",
doi = "10.1021/ja0680360",
language = "English",
volume = "129",
pages = "12713--12733",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "42",

}

TY - JOUR

T1 - Diverse stereocontrol effects induced by weakly coordinating anions. Stereospecific olefin polymerization pathways at archetypal Cs- and C1-symmetric metallocenium catalysts using mono- and polynuclear halo-perfluoroarylmetalates as cocatalysts

AU - Roberts, John

AU - Chen, Ming Chou

AU - Seyam, Afif M.

AU - Li, Ting

AU - Zuccaccia, Cristiano

AU - Stahl, Nicholas G.

AU - Marks, Tobin J

PY - 2007/10/24

Y1 - 2007/10/24

N2 - Counteranion effects on propylene polymerization rates and stereoselectivities are compared using Cs-symmetric Me 2C(Cp)(Flu)ZrMe2 (1; Cp = C5H 4,η5-cyclopentadienyl; Flu = C13H 8, η5-fluorenyl) and C1-symmetric Me 2Si(OHF)(CpR*)ZrMe2 (2; OHF = C13H 16, η5-octahydrofluorenyl; CpR* = η5-3-(-)-menthylcyclopentadienyl) precatalysts activated with the mononuclear and polynuclear perfluoroarylborate, -aluminate, and -gallate cocatalysts/activators B(C6F5)3 (3), B(o-C 6F5C6F4)3 (4), AI(C 6F5)3 (5), Ph3C+B(C 6F5)4- (6) Ph3C +FAI(o-C6F5C6F4) 3- (7), Ga(C6F5)3 (8), and recently reported mono- and polymetallic trityl perfluoroarylhalometalates Ph3C+FB(C6F5)3 - (9), Ph3C+FB(o-C6F 5C6F4)3- (10), (Ph 3C-)xF x[AI(C6F 5)3]yx- (x = 1, y = 1, 11; X = 1, y = 2, 12; x = 2, y = 3, 13), Ph3C+(C6F 5)3AIFAI(o-C6F5C6F 4)3- (14), Ph3C +XAI(C6F5)3- (X = Cl, 15; X = Br, 16), and Ph3C+F[Ga(C6F 5)3]2- (17). Temperature, propylene concentration, and solvent polarity dependence are surveyed in polymerizations catalyzed by 1 activated with cocatalysts 3-16 and with a 1:2 ratio of Ph 3CCI and 5, and with a 1:2 ratio of Ph3CBr and 5, and by 2 activated with 3, 6, 7, 12, and 14. Remarkable stereocontrol with high activities is observed for 1 + 12 and 1 + 14. Polypropylene samples produced using C1-symmetric precatalyst 2 are subjected to microstructural analyses using stochastic models describing the relative contributions of enantiofacial misinsertion and backskip processes. A powerful technique is introduced for calculating interparametric correlation matrices for these nonlinear stochastic models. The collected results significantly extend what is known about ion-pairing effects in the case of Cs-symmetric precatalyst 1 and allow these findings to be applied to the case of C 1-symmetric precatalyst 2 as an agent of isospecific propylene polymerization.

AB - Counteranion effects on propylene polymerization rates and stereoselectivities are compared using Cs-symmetric Me 2C(Cp)(Flu)ZrMe2 (1; Cp = C5H 4,η5-cyclopentadienyl; Flu = C13H 8, η5-fluorenyl) and C1-symmetric Me 2Si(OHF)(CpR*)ZrMe2 (2; OHF = C13H 16, η5-octahydrofluorenyl; CpR* = η5-3-(-)-menthylcyclopentadienyl) precatalysts activated with the mononuclear and polynuclear perfluoroarylborate, -aluminate, and -gallate cocatalysts/activators B(C6F5)3 (3), B(o-C 6F5C6F4)3 (4), AI(C 6F5)3 (5), Ph3C+B(C 6F5)4- (6) Ph3C +FAI(o-C6F5C6F4) 3- (7), Ga(C6F5)3 (8), and recently reported mono- and polymetallic trityl perfluoroarylhalometalates Ph3C+FB(C6F5)3 - (9), Ph3C+FB(o-C6F 5C6F4)3- (10), (Ph 3C-)xF x[AI(C6F 5)3]yx- (x = 1, y = 1, 11; X = 1, y = 2, 12; x = 2, y = 3, 13), Ph3C+(C6F 5)3AIFAI(o-C6F5C6F 4)3- (14), Ph3C +XAI(C6F5)3- (X = Cl, 15; X = Br, 16), and Ph3C+F[Ga(C6F 5)3]2- (17). Temperature, propylene concentration, and solvent polarity dependence are surveyed in polymerizations catalyzed by 1 activated with cocatalysts 3-16 and with a 1:2 ratio of Ph 3CCI and 5, and with a 1:2 ratio of Ph3CBr and 5, and by 2 activated with 3, 6, 7, 12, and 14. Remarkable stereocontrol with high activities is observed for 1 + 12 and 1 + 14. Polypropylene samples produced using C1-symmetric precatalyst 2 are subjected to microstructural analyses using stochastic models describing the relative contributions of enantiofacial misinsertion and backskip processes. A powerful technique is introduced for calculating interparametric correlation matrices for these nonlinear stochastic models. The collected results significantly extend what is known about ion-pairing effects in the case of Cs-symmetric precatalyst 1 and allow these findings to be applied to the case of C 1-symmetric precatalyst 2 as an agent of isospecific propylene polymerization.

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