Issue 11, 2003
From the journal:

Dalton Transactions

Silsesquioxane-bonded zirconocene complexes; soluble models for silica-tethered olefin polymerization catalysts†

John R. Severn,a   Robbert Duchateau,*a   Rutger A. van Santen,b   Dianne D. Ellis,c   Anthony L. Spekc  and  Glenn P. A. Yapd  

* Corresponding authors

a Department of Polymer Chemistry/Dutch Polymer Institute, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven, The Netherlands

b Schuit Institute of Catalysis, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven, The Netherlands

c Department of Crystal and Structural Chemistry, Utrecht University, Padualaan 8, 3584 CH Utrecht, The Netherlands

d University of Ottawa, Ontario, K1N 6N5 Ottawa, Canada

Abstract

Silsesquioxane tethered fluorene ligands [R7Si8O12X]-9-Flu(H) (R = c-C6H11, X = – (1); R = c-C5H9, X = CH2 (2), (CH2)3 (3), C6H4CH2 (4)), (c-C5H9)7Si8O12CH2-9-Flu(9-EMe3) (E = Si (5a), Sn (5b)) and zirconium dichlorides Cp″[(c-C5H9)7Si8O12CH2-9-Flu]ZrCl2 (6b, Cp″ = 1,3-C5H3(SiMe3)2), Cp*[(c-C5H9)7Si8O12-X-9-Flu]ZrCl2 (X = CH2 (6a), (CH2)3 (7), C6H4CH2 (8)) and [(c-C5H9)7Si8O12CH2-9-Flu]2ZrCl2 (9) have been applied as models for silica-tethered ancillary ligands and silica tethered-zirconocenes. Immobilization of zirconocenes containing a pendant anchorable functionality, Cp″[Me2(EtO)SiCH2Flu]ZrCl2 (10) and Cp[C5Me4SiMe2OEt]ZrCl2 (11) was considerably hampered by competitive Zr–Cl and Si–OEt bond splitting. When activated with MAO (methylalumoxane), 6–9 yield active ethylene polymerization systems.

Graphical abstract: Silsesquioxane-bonded zirconocene complexes; soluble models for silica-tethered olefin polymerization catalysts

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Article information

DOI
https://doi.org/10.1039/B300698K
Article type
Paper
Submitted
17 Jan 2003
Accepted
10 Apr 2003
First published
29 Apr 2003

Dalton Trans., 2003, 2293-2302

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Silsesquioxane-bonded zirconocene complexes; soluble models for silica-tethered olefin polymerization catalysts

J. R. Severn, R. Duchateau, R. A. van Santen, D. D. Ellis, A. L. Spek and G. P. A. Yap, Dalton Trans., 2003, 2293 DOI: 10.1039/B300698K

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