'Tucked-in' titanocene alkyls and alkylidenes

被引：17

作者：

van der Heijden, H

Hessen, B

机构：

[1] Univ Groningen, Ctr Catalyt Olefin Polymerisat, Stratingh Inst Chem & Chem Engn, NL-9747 AG Groningen, Netherlands

[2] Shell Res & Technol Ctr Amsterdam, NL-1031 CA Amsterdam, Netherlands

来源：

INORGANICA CHIMICA ACTA | 2003年 / 345卷

关键词：

alkylidene; C-H bond activation; titanium; alkyne; ethene;

D O I：

10.1016/S0020-1693(02)01282-3

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Titanocene neopentyl complexes with one cyclometallated tert-butylcyclopentadienyl group, (eta(5)-C5H4R)(eta(5),eta(1)-C5H4CMe2CH2)Ti(CHCMe3) are readily obtained from the corresponding titanocene dichlorides and bis(neopentyl)magnesium. These compounds lose neopentane by a-H abstraction from the cyclometallated ligand to generate alkylidene species in which the alkylidene moiety is connected to one of the cyclopentadienyl ligands. The alkylidene (C5H4Me)(C5H4CMe2CH)Ti(PMe3) reacts with benzene-d(6) by stereoselective addition of a C-D bond across the Ti=C bond. These 'tucked-in' alkylidene species also exhibit a wide range of reactivity towards unsaturated substrates (alkynes, ethene, benzonitrile), initiated by cycloaddition to the Ti=C bond. (C) 2002 Elsevier Science B.V. All rights reserved.

引用

页码：27 / 36

页数：10

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