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

来源：

ORGANOMETALLICS | 2004年 / 23卷 / 01期

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.

引用

页码：149 / 152

页数：4

共 17 条

[11]

Kaminsky W., 1999, METALORGANIC CATALYS

[12] Group 4 ansa-cyclopentadienyl-amido catalysts for olefin polymerization [J].

McKnight, AL ;

Waymouth, RM .

CHEMICAL REVIEWS, 1998, 98 (07) :2587-2598

[13]

Stevens J. C., 1991, Eur. Pat. Appl., Patent No. [EP 416815-A2, 416815, 0416815]

[14] 1H NMR characterization of intermediates formed by the activation of zirconocenes with methylaluminoxane at high Al/Zr ratios [J].

Talsi, EP ;

Bryliakov, KP ;

Semikolenova, NV ;

Zakharova, VA ;

Ystenes, M ;

Rytter, E .

MENDELEEV COMMUNICATIONS, 2003, (02) :46-48

[15] NMR-STUDY OF THE REACTIONS IN CP(2)TIMECL/ALME(3) AND CP(2)TIMECL/METHYLALUMOXANE SYSTEMS, CATALYSTS FOR OLEFIN POLYMERIZATION [J].

TRITTO, I ;

SACCHI, MC ;

LI, SX .

MACROMOLECULAR RAPID COMMUNICATIONS, 1994, 15 (03) :217-223

[16] Dimethylzirconocene-methylaluminoxane catalyst for olefin polymerization: NMR study of reaction equilibria [J].

Tritto, I ;

Donetti, R ;

Sacchi, MC ;

Locatelli, P ;

Zannoni, G .

MACROMOLECULES, 1997, 30 (05) :1247-1252

[17] METALLOCENE ION-PAIRS - A DIRECT INSIGHT INTO THE REACTION EQUILIBRIA AND POLYMERIZATION BY C-13 NMR-SPECTROSCOPY [J].

TRITTO, I ;

SACCHI, MC ;

LOCATELLI, P ;

LI, SX .

MACROMOLECULAR SYMPOSIA, 1995, 89 :289-298

← 1 2 →