Heterogeneous self-supported dirhodium(II) catalysts with high catalytic efficiency in cyclopropanation - a structural study

被引：22

作者：

Liu, Jiquan ^{[1
]}

Fasel, Claudia ^{[2
]}

Braga-Groszewicz, Pedro ^{[1
]}

Rothermel, Niels ^{[1
]}

Thankamony, Aany Sofia Lilly ^{[1
]}

Sauer, Grit ^{[1
]}

Xu, Yeping ^{[1
]}

Gutmann, Torsten ^{[1
]}

Buntkowsky, Gerd ^{[1
]}

机构：

[1] Tech Univ Darmstadt, Eduard Zintl Inst Inorgan Chem & Phys Chem, Alarich Weiss Str 8, D-64287 Darmstadt, Germany

[2] Tech Univ Darmstadt, FB Mat & Geowissensch, Alarich Weiss Str 2, D-64287 Darmstadt, Germany

来源：

CATALYSIS SCIENCE & TECHNOLOGY | 2016年 / 6卷 / 21期

关键词：

METAL-ORGANIC FRAMEWORKS; RHODIUM(II) ACETATE; COORDINATION POLYMER; ASYMMETRIC CYCLOPROPANATION; RECYCLABLE CATALYST; HYDROGEN STORAGE; DIAZO-COMPOUNDS; COMPLEX; DESIGN; OXIDATION;

D O I：

10.1039/c6cy00915h

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Catalytically active dirhodium sheet-like coordination polymers are synthesized from their precursors via ligand exchange. The individual lamellae of the dirhodium-bdc frameworks are stacked as parallel sheets, which are randomly oriented or slightly ordered. As inorganic building blocks Rh-2(TFA)(4) and Rh-2(OAc)(4), and as organic linker benzene 1,4-dicarboxylate (bdc) are employed. The successful synthesis of the Rh-2-bdc(Tf) and Rh-2-bdc(Ac) catalysts is proven by ATR-IR, XPS and C-13 CP MAS NMR. Residual trifluoroacetate species are investigated by quantitative F-19 MAS NMR which further reflects the configuration of trifluoroacetate in the obtained Rh-2-bdc(Tf), and defects in the structure. DR-UV-vis and XPS demonstrate that the oxidation state and the Rh-Rh single bond in the dirhodium node are maintained during the ligand substitution process. The stability and reusability of the catalysts are verified by TG-DTA measurements and leaching tests. The catalysts show similar catalytic efficiency as the homogeneous catalyst in the model cyclopropanation between ethyl diazoacetate (EDA) and styrene.

引用

页码：7830 / 7840

页数：11

共 94 条

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