Synthesis, characterization, and activity in ethylene polymerization of silica supported cationic cyclopentadienyl zirconium complexes

Nicolas Millot; Sophie Soignier; Catherine C. Santini; Anne Baudouin; Jean Marie Basset

doi:10.1021/ja060420+

Synthesis, characterization, and activity in ethylene polymerization of silica supported cationic cyclopentadienyl zirconium complexes

Nicolas Millot, Sophie Soignier, Catherine C. Santini^*, Anne Baudouin, Jean Marie Basset

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

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Abstract

Cp*ZrMe₃ reacts with silica pretreated at 800 °C, SiO_2-(800) through two pathways: (a) protolysis of a Zr-Me group by surface silanols and (b) transfer of a methyl group to the surface by opening of strained siloxane bridges, in a relative proportion of ca. 9/1, respectively, affording a well-defined surface species [(≡SiO)ZrCp*(Me) ₂], 3, but with two different local environments 3a, [(≡SiO)ZrCp*(Me)₂][≡Si-O-Si≡], and the other with 3b, (Equation presented) The reaction of the species 3 with B(C ₆F₅)₃ is controlled by this local environment and gives three surface species [(≡SiO)ZrCp*(Me)] ⁺[MeB(C₆F₅)₃]^- [≡Si-O-Si≡], 4a (20%), [(≡SiO)ZrCp*(Me)] ⁺[(Me)B(C₆F₅)₃]^- [≡Si-Me], 4b (10%), and [(≡SiO)₂ZrCp*] ⁺[(Me)B(C₆F₅)₃] ^-[≡Si-O-Si≡], 5 (70%). On the contrary, the reaction of Cp*Zr(Me)₃, Cp₂Zr(Me)₂ with [≡SiO-B(C₆F₅)₃]^-[HNEt ₂Ph]⁺, 6, leads to a unique species [(≡SiO)B(C ₆F₅)₃]_-[Cp*Zr(Me) ₂-NEt₂Ph]₊, 7, and [(≡SiO)ZrCp ₂]⁺[(Me)B(C₆F₅)₃] ^-, 9 respectively. The complexes 4 and 7 are active catalysts in ethylene polymerization at room temperature, 93 and 67 kg PE mol Zr^1- atm^-1 bar^-1, respectively, indicating that covalently bounded Zr catalyst 4 is slightly more active than the "floating" cationic catalyst 7.

Original language	English (US)
Pages (from-to)	9361-9370
Number of pages	10
Journal	Journal of the American Chemical Society
Volume	128
Issue number	29
DOIs	https://doi.org/10.1021/ja060420+
State	Published - Jul 26 2006
Externally published	Yes

ASJC Scopus subject areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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@article{1c4dd93554f24366b52bde7db3543e3d,

title = "Synthesis, characterization, and activity in ethylene polymerization of silica supported cationic cyclopentadienyl zirconium complexes",

abstract = "Cp*ZrMe3 reacts with silica pretreated at 800 °C, SiO2-(800) through two pathways: (a) protolysis of a Zr-Me group by surface silanols and (b) transfer of a methyl group to the surface by opening of strained siloxane bridges, in a relative proportion of ca. 9/1, respectively, affording a well-defined surface species [(≡SiO)ZrCp*(Me) 2], 3, but with two different local environments 3a, [(≡SiO)ZrCp*(Me)2][≡Si-O-Si≡], and the other with 3b, (Equation presented) The reaction of the species 3 with B(C 6F5)3 is controlled by this local environment and gives three surface species [(≡SiO)ZrCp*(Me)] +[MeB(C6F5)3]- [≡Si-O-Si≡], 4a (20%), [(≡SiO)ZrCp*(Me)] +[(Me)B(C6F5)3]- [≡Si-Me], 4b (10%), and [(≡SiO)2ZrCp*] +[(Me)B(C6F5)3] -[≡Si-O-Si≡], 5 (70%). On the contrary, the reaction of Cp*Zr(Me)3, Cp2Zr(Me)2 with [≡SiO-B(C6F5)3]-[HNEt 2Ph]+, 6, leads to a unique species [(≡SiO)B(C 6F5)3]-[Cp*Zr(Me) 2-NEt2Ph]+, 7, and [(≡SiO)ZrCp 2]+[(Me)B(C6F5)3] -, 9 respectively. The complexes 4 and 7 are active catalysts in ethylene polymerization at room temperature, 93 and 67 kg PE mol Zr1- atm-1 bar-1, respectively, indicating that covalently bounded Zr catalyst 4 is slightly more active than the {"}floating{"} cationic catalyst 7.",

author = "Nicolas Millot and Sophie Soignier and Santini, {Catherine C.} and Anne Baudouin and Basset, {Jean Marie}",

year = "2006",

month = jul,

day = "26",

doi = "10.1021/ja060420+",

language = "English (US)",

volume = "128",

pages = "9361--9370",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

number = "29",

}

TY - JOUR

T1 - Synthesis, characterization, and activity in ethylene polymerization of silica supported cationic cyclopentadienyl zirconium complexes

AU - Millot, Nicolas

AU - Soignier, Sophie

AU - Santini, Catherine C.

AU - Baudouin, Anne

AU - Basset, Jean Marie

PY - 2006/7/26

Y1 - 2006/7/26

N2 - Cp*ZrMe3 reacts with silica pretreated at 800 °C, SiO2-(800) through two pathways: (a) protolysis of a Zr-Me group by surface silanols and (b) transfer of a methyl group to the surface by opening of strained siloxane bridges, in a relative proportion of ca. 9/1, respectively, affording a well-defined surface species [(≡SiO)ZrCp*(Me) 2], 3, but with two different local environments 3a, [(≡SiO)ZrCp*(Me)2][≡Si-O-Si≡], and the other with 3b, (Equation presented) The reaction of the species 3 with B(C 6F5)3 is controlled by this local environment and gives three surface species [(≡SiO)ZrCp*(Me)] +[MeB(C6F5)3]- [≡Si-O-Si≡], 4a (20%), [(≡SiO)ZrCp*(Me)] +[(Me)B(C6F5)3]- [≡Si-Me], 4b (10%), and [(≡SiO)2ZrCp*] +[(Me)B(C6F5)3] -[≡Si-O-Si≡], 5 (70%). On the contrary, the reaction of Cp*Zr(Me)3, Cp2Zr(Me)2 with [≡SiO-B(C6F5)3]-[HNEt 2Ph]+, 6, leads to a unique species [(≡SiO)B(C 6F5)3]-[Cp*Zr(Me) 2-NEt2Ph]+, 7, and [(≡SiO)ZrCp 2]+[(Me)B(C6F5)3] -, 9 respectively. The complexes 4 and 7 are active catalysts in ethylene polymerization at room temperature, 93 and 67 kg PE mol Zr1- atm-1 bar-1, respectively, indicating that covalently bounded Zr catalyst 4 is slightly more active than the "floating" cationic catalyst 7.

AB - Cp*ZrMe3 reacts with silica pretreated at 800 °C, SiO2-(800) through two pathways: (a) protolysis of a Zr-Me group by surface silanols and (b) transfer of a methyl group to the surface by opening of strained siloxane bridges, in a relative proportion of ca. 9/1, respectively, affording a well-defined surface species [(≡SiO)ZrCp*(Me) 2], 3, but with two different local environments 3a, [(≡SiO)ZrCp*(Me)2][≡Si-O-Si≡], and the other with 3b, (Equation presented) The reaction of the species 3 with B(C 6F5)3 is controlled by this local environment and gives three surface species [(≡SiO)ZrCp*(Me)] +[MeB(C6F5)3]- [≡Si-O-Si≡], 4a (20%), [(≡SiO)ZrCp*(Me)] +[(Me)B(C6F5)3]- [≡Si-Me], 4b (10%), and [(≡SiO)2ZrCp*] +[(Me)B(C6F5)3] -[≡Si-O-Si≡], 5 (70%). On the contrary, the reaction of Cp*Zr(Me)3, Cp2Zr(Me)2 with [≡SiO-B(C6F5)3]-[HNEt 2Ph]+, 6, leads to a unique species [(≡SiO)B(C 6F5)3]-[Cp*Zr(Me) 2-NEt2Ph]+, 7, and [(≡SiO)ZrCp 2]+[(Me)B(C6F5)3] -, 9 respectively. The complexes 4 and 7 are active catalysts in ethylene polymerization at room temperature, 93 and 67 kg PE mol Zr1- atm-1 bar-1, respectively, indicating that covalently bounded Zr catalyst 4 is slightly more active than the "floating" cationic catalyst 7.

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U2 - 10.1021/ja060420+

DO - 10.1021/ja060420+

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C2 - 16848471

AN - SCOPUS:33746342816

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JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

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ER -

Synthesis, characterization, and activity in ethylene polymerization of silica supported cationic cyclopentadienyl zirconium complexes

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