Cationic metallocene polymerization catalysts based on tetrakis(pentafluorophenyl)borate and its derivatives. probing the limits of anion "noncoordination" via a synthetic, solution dynamic, structural, and catalytic olefin polymerization study

Li Jia, Xinmin Yang, Charlotte L. Stern, Tobin J Marks

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Abstract

The synthesis and properties of two soluble, weakly coordinating derivatives of the tetrakis-(perfluoroaryl)borate anion B(4-C6F4TBS)4- and B(4-C6F4TIPS)4- (TBS = tert-butyldimethylsilyl and TIPS = triisopropylsilyl) are reported. Reaction of the trityl salts of the above anions with a variety of zirconium and thorium L2MMe2 complexes in benzene or toluene affords the cationic ion-paired methyl complexes L2MMe+X- or the corresponding hydrido complexes L2MH+X- (L2 = bis(cyclopentadienyl)- or cyclopentadienylamido-type ligand) when the reaction is carried out under dihydrogen. The solid state structure of the complex (Me5Cp)2ThMe+B(C6F5) 4- has been characterized by X-ray diffraction. The B(C6F5)4--based zirconocenium methyl complexes L2MMe+ are unstable at room temperature with respect to, among other factors, intramolecular C-H activation of the ligand framework. In general, the thermal stabilities of the B(C6F4TBS)4-- and B(C6F4TIPS)4--derived complexes are greater than those of the corresponding B(C6F5)4-- and MeB(C6F5)3--derived analogues. The relative coordinative tendencies of MeB(C6F5)3-, B(C6F5)4-, B(C6F4TBS)4-, and B(C6F4TIPS)4- are estimated from the solution spectroscopic information and the structural dynamics of the ion-pairs and follow the order MeB(C6F5)3- > B(C6F4TBS)4- ≈ B(C6F4TIPS)4- > B(C6F5)4-. The coordination of the neutral metallocene precursors to the cationic metallocenes is found to compete with counteranion coordination. Arene solvent coordination to the zirconium constrained geometry cation [(Me4Cp)SiMe2(NtBu)]ZrMe+ is also observed when B(C6F5)4- is the counteranion. (1,2-Me2Cp)2ZrMe+B(C6F 4TBS)4- undergoes slow decomposition under an inert atmosphere to afford [(1,2-Me2Cp)2ZrF]2(μ-F)+B(C 6F4TBS)4-, which has been characterized by X-ray diffraction. The olefin polymerization activity and thermal stability of the zirconocene catalysts reaches a maximum when B(C6F4TBS)4- and B(C6F4TIPS)4- are used as counteranions. The polymerization activity of the zirconium constrained geometry complex also reaches a maximum in aromatic solvents when B(C6F5)4- is used as the counteranion, apparently due to solvent coordination.

Original languageEnglish
Pages (from-to)842-857
Number of pages16
JournalOrganometallics
Volume16
Issue number5
Publication statusPublished - 1997

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Cationic polymerization
dynamic structural analysis
Structural dynamics
Alkenes
borates
alkenes
Anions
polymerization
Polymerization
anions
Derivatives
catalysts
Catalysts
Thermodynamic stability
Ions
Thorium
Ligands
X ray diffraction
Borates
thermal stability

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

@article{41671c2fc0244b3fa6681318e35bef6e,
title = "Cationic metallocene polymerization catalysts based on tetrakis(pentafluorophenyl)borate and its derivatives. probing the limits of anion {"}noncoordination{"} via a synthetic, solution dynamic, structural, and catalytic olefin polymerization study",
abstract = "The synthesis and properties of two soluble, weakly coordinating derivatives of the tetrakis-(perfluoroaryl)borate anion B(4-C6F4TBS)4- and B(4-C6F4TIPS)4- (TBS = tert-butyldimethylsilyl and TIPS = triisopropylsilyl) are reported. Reaction of the trityl salts of the above anions with a variety of zirconium and thorium L2MMe2 complexes in benzene or toluene affords the cationic ion-paired methyl complexes L2MMe+X- or the corresponding hydrido complexes L2MH+X- (L2 = bis(cyclopentadienyl)- or cyclopentadienylamido-type ligand) when the reaction is carried out under dihydrogen. The solid state structure of the complex (Me5Cp)2ThMe+B(C6F5) 4- has been characterized by X-ray diffraction. The B(C6F5)4--based zirconocenium methyl complexes L2MMe+ are unstable at room temperature with respect to, among other factors, intramolecular C-H activation of the ligand framework. In general, the thermal stabilities of the B(C6F4TBS)4-- and B(C6F4TIPS)4--derived complexes are greater than those of the corresponding B(C6F5)4-- and MeB(C6F5)3--derived analogues. The relative coordinative tendencies of MeB(C6F5)3-, B(C6F5)4-, B(C6F4TBS)4-, and B(C6F4TIPS)4- are estimated from the solution spectroscopic information and the structural dynamics of the ion-pairs and follow the order MeB(C6F5)3- > B(C6F4TBS)4- ≈ B(C6F4TIPS)4- > B(C6F5)4-. The coordination of the neutral metallocene precursors to the cationic metallocenes is found to compete with counteranion coordination. Arene solvent coordination to the zirconium constrained geometry cation [(Me4Cp)SiMe2(NtBu)]ZrMe+ is also observed when B(C6F5)4- is the counteranion. (1,2-Me2Cp)2ZrMe+B(C6F 4TBS)4- undergoes slow decomposition under an inert atmosphere to afford [(1,2-Me2Cp)2ZrF]2(μ-F)+B(C 6F4TBS)4-, which has been characterized by X-ray diffraction. The olefin polymerization activity and thermal stability of the zirconocene catalysts reaches a maximum when B(C6F4TBS)4- and B(C6F4TIPS)4- are used as counteranions. The polymerization activity of the zirconium constrained geometry complex also reaches a maximum in aromatic solvents when B(C6F5)4- is used as the counteranion, apparently due to solvent coordination.",
author = "Li Jia and Xinmin Yang and Stern, {Charlotte L.} and Marks, {Tobin J}",
year = "1997",
language = "English",
volume = "16",
pages = "842--857",
journal = "Organometallics",
issn = "0276-7333",
publisher = "American Chemical Society",
number = "5",

}

TY - JOUR

T1 - Cationic metallocene polymerization catalysts based on tetrakis(pentafluorophenyl)borate and its derivatives. probing the limits of anion "noncoordination" via a synthetic, solution dynamic, structural, and catalytic olefin polymerization study

AU - Jia, Li

AU - Yang, Xinmin

AU - Stern, Charlotte L.

AU - Marks, Tobin J

PY - 1997

Y1 - 1997

N2 - The synthesis and properties of two soluble, weakly coordinating derivatives of the tetrakis-(perfluoroaryl)borate anion B(4-C6F4TBS)4- and B(4-C6F4TIPS)4- (TBS = tert-butyldimethylsilyl and TIPS = triisopropylsilyl) are reported. Reaction of the trityl salts of the above anions with a variety of zirconium and thorium L2MMe2 complexes in benzene or toluene affords the cationic ion-paired methyl complexes L2MMe+X- or the corresponding hydrido complexes L2MH+X- (L2 = bis(cyclopentadienyl)- or cyclopentadienylamido-type ligand) when the reaction is carried out under dihydrogen. The solid state structure of the complex (Me5Cp)2ThMe+B(C6F5) 4- has been characterized by X-ray diffraction. The B(C6F5)4--based zirconocenium methyl complexes L2MMe+ are unstable at room temperature with respect to, among other factors, intramolecular C-H activation of the ligand framework. In general, the thermal stabilities of the B(C6F4TBS)4-- and B(C6F4TIPS)4--derived complexes are greater than those of the corresponding B(C6F5)4-- and MeB(C6F5)3--derived analogues. The relative coordinative tendencies of MeB(C6F5)3-, B(C6F5)4-, B(C6F4TBS)4-, and B(C6F4TIPS)4- are estimated from the solution spectroscopic information and the structural dynamics of the ion-pairs and follow the order MeB(C6F5)3- > B(C6F4TBS)4- ≈ B(C6F4TIPS)4- > B(C6F5)4-. The coordination of the neutral metallocene precursors to the cationic metallocenes is found to compete with counteranion coordination. Arene solvent coordination to the zirconium constrained geometry cation [(Me4Cp)SiMe2(NtBu)]ZrMe+ is also observed when B(C6F5)4- is the counteranion. (1,2-Me2Cp)2ZrMe+B(C6F 4TBS)4- undergoes slow decomposition under an inert atmosphere to afford [(1,2-Me2Cp)2ZrF]2(μ-F)+B(C 6F4TBS)4-, which has been characterized by X-ray diffraction. The olefin polymerization activity and thermal stability of the zirconocene catalysts reaches a maximum when B(C6F4TBS)4- and B(C6F4TIPS)4- are used as counteranions. The polymerization activity of the zirconium constrained geometry complex also reaches a maximum in aromatic solvents when B(C6F5)4- is used as the counteranion, apparently due to solvent coordination.

AB - The synthesis and properties of two soluble, weakly coordinating derivatives of the tetrakis-(perfluoroaryl)borate anion B(4-C6F4TBS)4- and B(4-C6F4TIPS)4- (TBS = tert-butyldimethylsilyl and TIPS = triisopropylsilyl) are reported. Reaction of the trityl salts of the above anions with a variety of zirconium and thorium L2MMe2 complexes in benzene or toluene affords the cationic ion-paired methyl complexes L2MMe+X- or the corresponding hydrido complexes L2MH+X- (L2 = bis(cyclopentadienyl)- or cyclopentadienylamido-type ligand) when the reaction is carried out under dihydrogen. The solid state structure of the complex (Me5Cp)2ThMe+B(C6F5) 4- has been characterized by X-ray diffraction. The B(C6F5)4--based zirconocenium methyl complexes L2MMe+ are unstable at room temperature with respect to, among other factors, intramolecular C-H activation of the ligand framework. In general, the thermal stabilities of the B(C6F4TBS)4-- and B(C6F4TIPS)4--derived complexes are greater than those of the corresponding B(C6F5)4-- and MeB(C6F5)3--derived analogues. The relative coordinative tendencies of MeB(C6F5)3-, B(C6F5)4-, B(C6F4TBS)4-, and B(C6F4TIPS)4- are estimated from the solution spectroscopic information and the structural dynamics of the ion-pairs and follow the order MeB(C6F5)3- > B(C6F4TBS)4- ≈ B(C6F4TIPS)4- > B(C6F5)4-. The coordination of the neutral metallocene precursors to the cationic metallocenes is found to compete with counteranion coordination. Arene solvent coordination to the zirconium constrained geometry cation [(Me4Cp)SiMe2(NtBu)]ZrMe+ is also observed when B(C6F5)4- is the counteranion. (1,2-Me2Cp)2ZrMe+B(C6F 4TBS)4- undergoes slow decomposition under an inert atmosphere to afford [(1,2-Me2Cp)2ZrF]2(μ-F)+B(C 6F4TBS)4-, which has been characterized by X-ray diffraction. The olefin polymerization activity and thermal stability of the zirconocene catalysts reaches a maximum when B(C6F4TBS)4- and B(C6F4TIPS)4- are used as counteranions. The polymerization activity of the zirconium constrained geometry complex also reaches a maximum in aromatic solvents when B(C6F5)4- is used as the counteranion, apparently due to solvent coordination.

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