5-Methoxy-Substituted Zirconium Bis-indenyl ansa-Complexes: Synthesis, Structure, and Catalytic Activity in the Polymerization and Copolymerization of Alkenes

被引：40

作者：

Nifant'ev, Ilya E. ^{[1
,2
]}

Ivchenko, Pavel V. ^{[1
]}

Bagrov, Vladimir V. ^{[1
]}

Churakov, Andrei V. ^{[3
]}

Mercandelli, Pierluigi ^{[4
]}

机构：

[1] Moscow MV Lomonosov State Univ, Dept Chem, Moscow 119991, Russia

[2] RAS, AV Topchiev Petrochem Synth Inst, Moscow 119991, Russia

[3] RAS, NS Kurnakov Gen & Inorgan Chem Inst, Moscow 119991, Russia

[4] Univ Milan, Dipartimento Chim Strutturale & Stereochim Inorga, I-20133 Milan, Italy

来源：

ORGANOMETALLICS | 2012年 / 31卷 / 14期

关键词：

C-1-SYMMETRIC HETEROCYCLIC ZIRCONOCENES; CRYSTAL-STRUCTURES; PROPYLENE POLYMERIZATION; ETHYLENE POLYMERIZATION; METALLOCENE; POLYPROPYLENE; DERIVATIVES; DICHLORIDE; PENTAMETHYLCYCLOPENTADIENYL; SUBSTITUENTS;

D O I：

10.1021/om300160v

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

A number of 2-methyl-4-aryl-5-methoxy-6-alkylindenes and C-2-symmetric Me2Si-bridged ansa-zirconocenes based on them were synthesized. Zirconocenes were obtained by means of highly effective and scalable racemo-selective synthetic approach based on the use of a Zr tert-butyl amide complex. The structure of mu-(bis-[eta(5)-6-tert-butyl-5-methoxy-2-methyl-4-tert-butylphenyl-H-1-inden-1-yl]-dimethylsilanediyl)dichlorozirconium(IV) (14) has been established with X-ray analysis. The introduction of a methoxy group into the indenyl fragment of zirconocene significantly improved its catalytic performance (i.e., its activity, stereoselectivity, molecular mass potential, and thermal stability) in the polymerization and copolymerization of propylene in comparison with the benchmark Spaleck-zirconocene. The role of the methoxy group is proposed to stabilize the cationic catalytic intermediates, which was confirmed using DFT calculations.

引用

页码：4962 / 4970

页数：9

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