Formation and structures of cationic zirconium complexes in ternary systems rac-(SBI)ZrX2/AlBui3/[CPh3][B(C6F5)4] (X = Cl, Me)

被引：32

作者：

Bryliakov, Konstantin P. ^{[1
]}

Talsi, Evgenii P.

Semikolenova, Nina V.

Zakharov, Vladimir A.

Brand, Joerg

Alonso-Moreno, Carlos

Bochmann, Manfred

机构：

[1] Russian Acad Sci, Siberian Branch, Boreskov Inst Catalysis, Novosibirsk 630090, Russia

[2] Novosibirsk State Univ, Dept Nat Sci, Novosibirsk 630090, Russia

[3] Univ Konstanz, Fachbereich Chem, D-78457 Constance, Germany

[4] Univ E Anglia, Sch Chem Sci & Pharma, Wolfson Mat & Catalysis Ctr, Norwich NR4 7TJ, Norfolk, England

来源：

JOURNAL OF ORGANOMETALLIC CHEMISTRY | 2007年 / 692卷 / 04期

基金：

英国工程与自然科学研究理事会;

关键词：

metallocenes; catalysis; activation; intermediate; triisobutyl aluminum; NMR;

D O I：

10.1016/j.jorganchem.2006.10.037

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Using C-13, H-1 and F-19 NMR spectroscopy, formation of cationic species was studied in ternary systems (SBI)ZrX2/AlBu3i/ [CPh3][B(C6F5)(4)] where X = Cl, Me [(SBI) = rac-Me2Si(Ind)(2)]. In the first system (X = Cl), the ion pair [(SBI)Zr(mu-Cl)(2)Zr(SBI)][B(C6F5)(4)](2) (IV) predominates at low Al/Zr ratios (Al/Zr < 10), whereas at higher Al/Zr ratios (>= 20) in the absence of monomer mainly [(SBI)Zr(p-H)(mu-C4H7)AlBu2i] [B(C6F5)(4)] (V) is formed. The binuclear complex [(SBI)Zr(mu-CI)(2)Zr(SBI)][B(C6F5)(4)](2) has been character ized crystallographically. Species V is also formed in the system X = Me at high Al/Zr ratios. In the presence of AlBu3i, IV displays activity in propylene polymerization and is the most likely precursor of the polymerizing species. Consistent mechanisms have been proposed for the reactions in these catalytic systems. (c) 2006 Elsevier B.V. All rights reserved.

引用

页码：859 / 868

页数：10

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