Cationic Silica-Supported N-Heterocyclic Carbene Tungsten Oxo Alkylidene Sites: Highly Active and Stable Catalysts for Olefin Metathesis

被引：76
作者：
Pucino, Margherita [1 ]
Mougel, Victor [1 ]
Schowner, Roman [2 ]
Fedorov, Alexey [1 ]
Buchmeiser, Michael R. [2 ]
Coperet, Christophe [1 ]
机构：
[1] ETH, Dept Chem & Appl Biosci, Vladimir Prelog Weg 2, CH-8093 Zurich, Switzerland
[2] Univ Stuttgart, Inst Polymer Chem, Pfaffenwaldring 55, D-70569 Stuttgart, Germany
来源：
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2016年 / 55卷 / 13期
基金：
瑞士国家科学基金会;
关键词：
metathesis; N-heterocyclic carbene; structure elucidation; supported catalysts; tungsten; SURFACE ORGANOMETALLIC CHEMISTRY; RING-OPENING/CROSS-METATHESIS; STATE NMR-SPECTROSCOPY; ALKENE METATHESIS; HETEROGENEOUS CATALYSTS; RUTHENIUM CATALYSTS; CLOSING METATHESIS; NOBEL LECTURE; COMPLEXES; MOLYBDENUM;
D O I：
10.1002/anie.201510678
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
Designing supported alkene metathesis catalysts with high activity and stability is still a challenge, despite significant advances in the last years. Described herein is the combination of strong sigma-donating N-heterocyclic carbene ligands with weak sigma-donating surface silanolates and cationic tungsten sites leading to highly active and stable alkene metathesis catalysts. These well-defined silica-supported catalysts, [(SiO)W(=O)(=CHCMe2Ph)(IMes)(OTf)] and [(SiO)W(=O)(=CHCMe2Ph)(IMes)(+)][B(Ar-F)(4)(-)] [IMes=1,3-bis(2,4,6-trimethylphenyl)-imidazol-2-ylidene, B(Ar-F)(4)=B(3,5-(CF3)(2)C6H3)(4)] catalyze alkene metathesis, and the cationic species display unprecedented activity for a broad range of substrates, especially for terminal olefins with turnover numbers above 1.2 million for propene.
引用
收藏
页码：4300 / 4302
页数：3
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