Redox Control of a Dendritic Ferrocenyl-Based Homogeneous Catalyst

被引：90

作者：

Neumann, Paul ^{[1
]}

Dib, Hanna ^{[2
]}

Caminade, Anne-Marie ^{[2
]}

Hey-Hawkins, Evamarie ^{[1
]}

机构：

[1] Univ Leipzig, Inst Inorgan Chem, D-04103 Leipzig, Germany

[2] CNRS, Lab Chim Coordinat, F-31077 Toulouse 4, France

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2015年 / 54卷 / 01期

关键词：

dendrimers; ferrocene; homogeneous catalysis; phosphanes; redox-switchable catalysis; TRANSITION-METAL-COMPLEXES; SWITCHABLE PHASE TAGS; ALLYLIC ALCOHOLS; CARBONYL-COMPOUNDS; POLYMERIZATION CATALYST; AQUEOUS-MEDIA; ISOMERIZATION; MECHANISM; KETONES; RHODIUM;

D O I：

10.1002/anie.201408314

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The application of a dendrimer in a redox-switchable catalytic process is reported. A monomeric and the corresponding dendritic ferrocenylphosphane ligand were used to develop well-defined controllable catalysts with distinct redox states. The corresponding ruthenium(II) complexes catalyze the isomerization of the allylic alcohol 1-octen-3-ol. By adding a chemical oxidant or reductant, it was possible to reversibly switch the catalytic activity of the complexes. On oxidation, the ferrocenium moiety withdraws electron density from the phosphane, thereby lowering its basicity. The resulting electron-poor ruthenium center shows much lower activity for the redox isomerization and the reaction rate is markedly reduced.

引用

页码：311 / 314

页数：4

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