Synthesis, characterization, and catalytic properties of ansa-zirconocenes [Zr{1-Me2Si(3-η5-C9H5R) 2}Cl2] (R = Me, nPr, nBu, and Bz)

Carlos Alonso-Moreno; Antonio Antiñolo; Fernando Carrillo-Hermosilla; Antonio Otero; Ana M. Rodríguez; José Sancho; Victoria Volkis; Moris Eisen

doi:10.1002/ejic.200500845

Synthesis, characterization, and catalytic properties of ansa-zirconocenes [Zr{1-Me₂Si(3-η⁵-C₉H₅R) ₂}Cl₂] (R = Me, nPr, nBu, and Bz)

Carlos Alonso-Moreno, Antonio Antiñolo, Fernando Carrillo-Hermosilla, Antonio Otero^*, Ana M. Rodríguez, José Sancho, Victoria Volkis, Moris Eisen

^*Corresponding author for this work

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

6 Scopus citations

Abstract

The ansa-indene ligands {1-Me₂Si(3-C₉H ₆R)₂} [R = Me (1), nPr (2), nBu (3), and Bz (4)] were prepared by alkylation of the unsubstituted ansa-indene. These ligands were converted, by reaction with nBuLi, to the di-lithium compounds [Li ₂{1-Me₂Si(3-C₉H₅R)₂}] [R = Me (5), nPr (6), nBu (7), and Bz (8)]. ansa-Zirconocenes, [Zr{1-Me ₂Si(3-η⁵-C₉H₅R) ₂}Cl₂] [R = Me (9), nPr (10), nBu (11), and Bz (12)], have been prepared by the reaction of ZrCl₄ with 5-8 in diethyl ether/toluene at -78°C. The molecular structure of meso-[Zr{1-Me ₂Si[3-η⁵-C₉H₅(CH ₃)]₂}Cl₂] (9) and rac-[Zr{1-Me ₂Si[3-η⁵-C₉H₅-(CH ₂CH₂CH₃)]₂}Cl₂] (10) have been determined by single-crystal X-ray diffraction studies. Ethylene polymerization catalysis has been studied for complexes 9-12 as a mixture of meso and rac isomers in the presence of methylaluminoxane (MAO) as cocatalyst. Complexes 9-12 exhibit high activities and give rise to polyethylene with low molecular weights without the introduction of molecular hydrogen. In addition, active species from these complexes were found to be very stable in comparison with unsubstituted analogues.

Original language	English
Pages (from-to)	972-979
Number of pages	8
Journal	European Journal of Inorganic Chemistry
Issue number	5
DOIs	https://doi.org/10.1002/ejic.200500845
State	Published - 6 Mar 2006
Externally published	Yes

Keywords

Ethylene
Homogeneous catalysis
Metallocenes
Polymerization
Zirconium

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10.1002/ejic.200500845

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@article{85219bb5f34040e3b8bb0db6ef783029,

title = "Synthesis, characterization, and catalytic properties of ansa-zirconocenes [Zr{1-Me2Si(3-η5-C9H5R) 2}Cl2] (R = Me, nPr, nBu, and Bz)",

abstract = "The ansa-indene ligands {1-Me2Si(3-C9H 6R)2} [R = Me (1), nPr (2), nBu (3), and Bz (4)] were prepared by alkylation of the unsubstituted ansa-indene. These ligands were converted, by reaction with nBuLi, to the di-lithium compounds [Li 2{1-Me2Si(3-C9H5R)2}] [R = Me (5), nPr (6), nBu (7), and Bz (8)]. ansa-Zirconocenes, [Zr{1-Me 2Si(3-η5-C9H5R) 2}Cl2] [R = Me (9), nPr (10), nBu (11), and Bz (12)], have been prepared by the reaction of ZrCl4 with 5-8 in diethyl ether/toluene at -78°C. The molecular structure of meso-[Zr{1-Me 2Si[3-η5-C9H5(CH 3)]2}Cl2] (9) and rac-[Zr{1-Me 2Si[3-η5-C9H5-(CH 2CH2CH3)]2}Cl2] (10) have been determined by single-crystal X-ray diffraction studies. Ethylene polymerization catalysis has been studied for complexes 9-12 as a mixture of meso and rac isomers in the presence of methylaluminoxane (MAO) as cocatalyst. Complexes 9-12 exhibit high activities and give rise to polyethylene with low molecular weights without the introduction of molecular hydrogen. In addition, active species from these complexes were found to be very stable in comparison with unsubstituted analogues.",

keywords = "Ethylene, Homogeneous catalysis, Metallocenes, Polymerization, Zirconium",

author = "Carlos Alonso-Moreno and Antonio Anti{\~n}olo and Fernando Carrillo-Hermosilla and Antonio Otero and Rodr{\'i}guez, {Ana M.} and Jos{\'e} Sancho and Victoria Volkis and Moris Eisen",

year = "2006",

month = mar,

day = "6",

doi = "10.1002/ejic.200500845",

language = "英语",

pages = "972--979",

journal = "European Journal of Inorganic Chemistry",

issn = "1434-1948",

publisher = "Wiley-VCH Verlag",

number = "5",

}

TY - JOUR

T1 - Synthesis, characterization, and catalytic properties of ansa-zirconocenes [Zr{1-Me2Si(3-η5-C9H5R) 2}Cl2] (R = Me, nPr, nBu, and Bz)

AU - Alonso-Moreno, Carlos

AU - Antiñolo, Antonio

AU - Carrillo-Hermosilla, Fernando

AU - Otero, Antonio

AU - Rodríguez, Ana M.

AU - Sancho, José

AU - Volkis, Victoria

AU - Eisen, Moris

PY - 2006/3/6

Y1 - 2006/3/6

N2 - The ansa-indene ligands {1-Me2Si(3-C9H 6R)2} [R = Me (1), nPr (2), nBu (3), and Bz (4)] were prepared by alkylation of the unsubstituted ansa-indene. These ligands were converted, by reaction with nBuLi, to the di-lithium compounds [Li 2{1-Me2Si(3-C9H5R)2}] [R = Me (5), nPr (6), nBu (7), and Bz (8)]. ansa-Zirconocenes, [Zr{1-Me 2Si(3-η5-C9H5R) 2}Cl2] [R = Me (9), nPr (10), nBu (11), and Bz (12)], have been prepared by the reaction of ZrCl4 with 5-8 in diethyl ether/toluene at -78°C. The molecular structure of meso-[Zr{1-Me 2Si[3-η5-C9H5(CH 3)]2}Cl2] (9) and rac-[Zr{1-Me 2Si[3-η5-C9H5-(CH 2CH2CH3)]2}Cl2] (10) have been determined by single-crystal X-ray diffraction studies. Ethylene polymerization catalysis has been studied for complexes 9-12 as a mixture of meso and rac isomers in the presence of methylaluminoxane (MAO) as cocatalyst. Complexes 9-12 exhibit high activities and give rise to polyethylene with low molecular weights without the introduction of molecular hydrogen. In addition, active species from these complexes were found to be very stable in comparison with unsubstituted analogues.

AB - The ansa-indene ligands {1-Me2Si(3-C9H 6R)2} [R = Me (1), nPr (2), nBu (3), and Bz (4)] were prepared by alkylation of the unsubstituted ansa-indene. These ligands were converted, by reaction with nBuLi, to the di-lithium compounds [Li 2{1-Me2Si(3-C9H5R)2}] [R = Me (5), nPr (6), nBu (7), and Bz (8)]. ansa-Zirconocenes, [Zr{1-Me 2Si(3-η5-C9H5R) 2}Cl2] [R = Me (9), nPr (10), nBu (11), and Bz (12)], have been prepared by the reaction of ZrCl4 with 5-8 in diethyl ether/toluene at -78°C. The molecular structure of meso-[Zr{1-Me 2Si[3-η5-C9H5(CH 3)]2}Cl2] (9) and rac-[Zr{1-Me 2Si[3-η5-C9H5-(CH 2CH2CH3)]2}Cl2] (10) have been determined by single-crystal X-ray diffraction studies. Ethylene polymerization catalysis has been studied for complexes 9-12 as a mixture of meso and rac isomers in the presence of methylaluminoxane (MAO) as cocatalyst. Complexes 9-12 exhibit high activities and give rise to polyethylene with low molecular weights without the introduction of molecular hydrogen. In addition, active species from these complexes were found to be very stable in comparison with unsubstituted analogues.

KW - Ethylene

KW - Homogeneous catalysis

KW - Metallocenes

KW - Polymerization

KW - Zirconium

UR - http://www.scopus.com/inward/record.url?scp=33644996885&partnerID=8YFLogxK

U2 - 10.1002/ejic.200500845

DO - 10.1002/ejic.200500845

M3 - 文章

AN - SCOPUS:33644996885

SN - 1434-1948

SP - 972

EP - 979

JO - European Journal of Inorganic Chemistry

JF - European Journal of Inorganic Chemistry

IS - 5

ER -

Synthesis, characterization, and catalytic properties of ansa-zirconocenes [Zr{1-Me₂Si(3-η⁵-C₉H₅R) ₂}Cl₂] (R = Me, nPr, nBu, and Bz)

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