[N,N'-BIS(TRIMETHYLSILYL)BENZAMIDINATO]TITANIUM AND [N,N'-BIS(TRIMETHYLSILYL)BENZAMIDINATO]ZIRCONIUM COMPOUNDS - SYNTHESIS AND AND APPLICATION AS PRECURSORS FOR THE SYNDIOSPECIFIC POLYMERIZATION OF STYRENE

被引：123

作者：

FLORES, JC

CHIEN, JCW

RAUSCH, MD

机构：

[1] UNIV MASSACHUSETTS,DEPT CHEM,AMHERST,MA 01003

[2] UNIV MASSACHUSETTS,DEPT POLYMER SCI & ENGN,AMHERST,MA 01003

来源：

ORGANOMETALLICS | 1995年 / 14卷 / 04期

关键词：

D O I：

10.1021/om00004a040

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Ti(O-i-Pr)(3)Cl reacts with Li[C6H5C(NSiMe(3))(2)]. Et(2)O to give [eta-C6H5C(NSiMe(3))(2)]Ti(O-i-Pr)(3) (1) in quantitative yield. Mild thermolysis of 1 promotes the elimination of C6H5CN to form Ti(O-i-Pr)(3)N(SiMe(3))(2) (2), which is also synthesized from the reaction of Ti(O-i-Pr)(3)Cl and Li[N(SiMe(3))(2)]. Et(2)O. Treatment of the dimer {[eta-C6H5C(NSiMe(3))(2)]TiCl3}(2) (3) With donor ligands produces the corresponding monomeric adducts [eta-C6H5C(NSiMe3)(2)]TiCl3 . L (L = THF (4); PMe(3) (5)). Partial alkylation of the dimer 3 with 2 equiv of methyllithium gives {[eta-C6H5C(NSiMe(3))(2)]Ti(Me)Cl-2}(2) (6); however, treatment with 6 equiv leads to the formation of the bis(benzamidinate) compound [eta-C6H5C(NSiMe(3))(2)](2)TiMe(2) (7). Compound 7 is synthesized in better yield by the reaction between [eta-C6H5C(NSiMe3)(2)]2TiCl2 (8) and methyllithium. The same reaction but with the zirconium dichloride analog [eta-C6H5(NSiMe(3))(2)]2ZrCl2 (9) also gives [eta-C6H5C(NSiMe3)(2)](2)ZrMe(2) (10) in good yield. The catalytic systems 1/methylaluminoxane (MAO), 3/MAO, 4/MAO, and 5/MAO are active for styrene polymerization, forming syndiotactic polymer in a highly stereospecific process. The systems 1/MAO, 3/MAO, 8/MAO, and 9/MAO show low activity as ethylene polymerization catalysts. The cationic systems 1/triisobutylaluminum (TIBA)/Ph(3)C(+)[B(C6F5)(4)](-) (11) or 7,10/11 were not effective as olefin polymerization catalysts.

引用

页码：1827 / 1833

页数：7

共 23 条

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