Cationic Alkylaluminum-Complexed Zirconocene Hydrides as Participants in Olefin Polymerization Catalysis

被引：39

作者：

Baldwin, Steven M. ^{[1
]}

Bercaw, John E. ^{[1
]}

Brintzinger, Hans H. ^{[2
]}

机构：

[1] CALTECH, Arnold & Mabel Beckman Labs Chem Synth, Pasadena, CA 91125 USA

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

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2010年 / 132卷 / 40期

关键词：

DIISOBUTYLALUMINUM HYDRIDE; ORGANOMETALLIC COMPOUNDS; GROUP-III; TRIISOBUTYLALUMINUM;

D O I：

10.1021/ja105040r

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The alkylaluminum-complexed zirconocene trihydride cation [(SBI)Zr(mu-H)(3)((AlBu2)-Bu-i)(2)](+), which is obtained by reaction of (SBI)ZrCl2 with [Ph3C][B(C6F5)(4)] and excess HAI(i)8u(2) in toluene solution, catalyzes the formation of isotactic polypropene when exposed to propene at -30 degrees C. This cation remains the sole observable species in catalyst systems free of AlMe compounds. In the presence of AlMe3, however, exposure to propene causes the trihydride cation to be completely converted, under concurrent consumption of all hydride species by propene hydroalumination, to the doubly Me-bridged cation [(SBI)Zr(mu-Me)(2)AlMe2](+). The latter then becomes the resting state for further propene polymerization, which produces, by chain transfer to Al, mainly AlMe2-capped isotactic polypropene.

引用

页码：13969 / 13971

页数：3

共 17 条

[11] Kinetics and mechanistic insight into propylene polymerization with different metallocenes and various aluminium alkyls as cocatalysts [J].

Kleinschmidt, R ;

van der Leek, Y ;

Reffke, M ;

Fink, G .

JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL, 1999, 148 (1-2) :29-41

[12] Metallocene-catalyzed alkene polymerization and the observation of Zr-allyls [J].

Landis, Clark R. ;

Christianson, Matthew D. .

PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 2006, 103 (42) :15349-15354

[13]

Negishi E, 2005, TOP ORGANOMETAL CHEM, V8, P139

[14] Mechanistic Detail Revealed via Comprehensive Kinetic Modeling of [rac-C2H4(1-indenyl)2ZrMe2]-Catalyzed 1-Hexene Polymerization [J].

Novstrup, Krista A. ;

Travia, Nicholas E. ;

Medvedev, Grigori A. ;

Stanciu, Corneliu ;

Switzer, Jeffrey M. ;

Thomson, Kendall T. ;

Delgass, W. Nicholas ;

Abu-Omar, Mahdi M. ;

Caruthers, James M. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2010, 132 (02) :558-566

[15]

OHNO R, 1994, Patent No. 0582480

[16] DFT Study on Mechanism of Olefin Hydroalumination by XAlBu2i in the Presence Of Cp2ZrCl2 Catalyst. I. Simulation of Intermediate Formation in Reaction of HAlBu2i with Cp2ZrCl2 [J].

Pankratyev, Evgeniy Yu. ;

Tyumkina, Tatyana V. ;

Parfenova, Lyudmila V. ;

Khalilov, Leonard M. ;

Khursan, Sergey L. ;

Dzhemilev, Usein M. .

ORGANOMETALLICS, 2009, 28 (04) :968-977

[17]

WANG S, 2005, Patent No. 20050070675

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