Formation of Tri- and Tetranuclear Titanacycles through Decamethyltitanocene-Mediated Intermolecular C-C Coupling of Dinitriles

被引：28

作者：

Becket, Lisanne ^{[1
]}

Arndt, Perdita ^{[1
]}

Spannenberg, Anke ^{[1
]}

Jiao, Haijun ^{[1
]}

Rosenthal, Uwe ^{[1
]}

机构：

[1] Univ Rostock, Leibniz Inst Katalyse eV, D-18059 Rostock, Germany

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2015年 / 54卷 / 18期

关键词：

C-C coupling; macrocycles; metallacycles; nitriles; titanocene; CRYSTAL-STRUCTURE; GROUP-4; METALLOCENES; NITRILE-NITRILE; COMPLEXES; REACTIVITY; TITANOCENE; MACROCYCLES; CHEMISTRY; LIGANDS; ALKYL;

D O I：

10.1002/anie.201500109

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The reactions of [Cp*Ti-2(eta(2)-Me(3)SiC(2)SiMe3)] (Cp*=eta(5)-pentamethylcyclopentadienyl) with various dicyano compounds were investigated. Nitrile-nitrile C-C couplings result in multinuclear complexes owing to the bifunctionality of the substrates. Applying 1,3-or 1,4-dicyanobenzene led to tri-and tetranuclear complexes of the rare 1-metalla-2,5-diaza-cyclopenta- 2,4-dienes. These are potential catalysts and were tested in the ring-opening polymerization of e-caprolactone. The reaction with adiponitrile as alkyl dinitrile afforded a trinuclear 1-metalla-2,5-diaza-cyclopent-3-ene through additional protonation of the nitrogen atoms. The structure and bonding of the products were investigated by X-ray crystallography and DFT analysis to understand the molecular organization in the macrocycles.

引用

页码：5523 / 5526

页数：4

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