1H and 13C NMR spectroscopic study of Titanium(IV) species formed by activation of Cp2TiCl2 and [(Me4C5)SiMe2NtBu]TiCl2 with methylaluminoxane (MAO)

被引:61
作者
Bryliakov, KP [1 ]
Talsi, EP
Bochmann, M
机构
[1] Russian Acad Sci, GK Boreskov Inst Catalysis, Siberian Branch, Novosibirsk 630090, Russia
[2] Novosibirsk State Univ, Dept Nat Sci, Novosibirsk 630090, Russia
[3] Univ E Anglia, Sch Chem Sci & Pharm, Wolfson Mat & Catalysis Ctr, Norwich NR4 7TJ, Norfolk, England
关键词
D O I
10.1021/om034026l
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Using C-13 and H-1 NMR spectroscopy, the products of the reaction of Cp2TiCl2 with methylaluminoxane (MAO) at Al:Ti ratios of 5:1 to 300:1 have been identified as Cp2TiMeCl, Cp2TiMe2, [Cp2TiMe(mu-Cl)Cp-2-TiCl](+)[Me-MAO]- (II1) [Cp2TiMe(mu-Cl)Cp2TiMe](+)[MeMAO] (II2), [Cp2TiMe(mu-Me)Cp2TiMe](+)[Me-MAO](-) (II3) the heterobinuclear ion pair [Cp2Ti(mu-Me)(2)AlMe2](+)[MeMAO]- (III), and a "zwitterion-like" intermediate, formulated as Cp2TiMe+<--Me-Al-MAO (IV). In contrast, [(Me4C5)(SiMe2NBu)-Bu-t]TiCl2\MAO gives only zwitterion-like, not heterobinuclear, species.
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页码:149 / 152
页数:4
相关论文
共 17 条
[1]  
Babushkin DE, 2000, MACROMOL CHEM PHYS, V201, P558, DOI 10.1002/(SICI)1521-3935(20000301)201:5<558::AID-MACP558>3.0.CO
[2]  
2-N
[3]   BASE-FREE CATIONIC 14-ELECTRON ALKYLS OF TI, ZR AND HF AS POLYMERIZATION CATALYSTS - A COMPARISON [J].
BOCHMANN, M ;
LANCASTER, SJ .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1992, 434 (01) :C1-C5
[4]   CATIONIC GROUP-IV METAL ALKYL COMPLEXES AND THEIR ROLE AS OLEFIN POLYMERIZATION CATALYSTS - THE FORMATION OF ETHYL-BRIDGED DINUCLEAR AND HETERODINUCLEAR ZIRCONIUM AND HAFNIUM COMPLEXES [J].
BOCHMANN, M ;
LANCASTER, SJ .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1995, 497 (1-2) :55-59
[5]   Cationic Group 4 metallocene complexes and their role in polymerisation catalysis: The chemistry of well defined Ziegler catalysts [J].
Bochmann, M .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1996, (03) :255-270
[6]  
BOCHMANN M, 1994, ANGEW CHEM INT EDIT, V15, P33
[7]  
BRITZINGER HH, 1995, ANGEW CHEM INT EDIT, V34, P1143
[8]   13C-NMR study of Ti(IV) species formed by Cp*TiMe3 and Cp*TiCl3 activation with methylaluminoxane (MAO) [J].
Bryliakov, KP ;
Semikolenova, NV ;
Zakharov, VA ;
Talsi, EP .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 2003, 683 (01) :23-28
[9]   Cocatalysts for metal-catalyzed olefin polymerization: Activators, activation processes, and structure-activity relationships [J].
Chen, EYX ;
Marks, TJ .
CHEMICAL REVIEWS, 2000, 100 (04) :1391-1434
[10]   Very large counteranion modulation of cationic metallocene polymerization activity and stereoregulation by a sterically congested (perfluoroaryl)fluoroaluminate [J].
Chen, YX ;
Stern, CL ;
Marks, TJ .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1997, 119 (10) :2582-2583