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

Liu, Jiquan and Fasel, Claudia and Braga-Groszewicz, Pedro and Rothermel, Niels and Lilly Thankamony, Aany Sofia and Sauer, Grit and Xu, Yeping and Gutmann, Torsten and Buntkowsky, Gerd (2016):
Heterogeneous self-supported dirhodium(ii) catalysts with high catalytic efficiency in cyclopropanation – a structural study.
In: Catal. Sci. Technol., Royal Society of Chemistry, pp. 7830-7840, 6, (21), ISSN 2044-4753,
[Online-Edition: http://dx.doi.org/10.1039/C6CY00915H],
[Article]

Abstract

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 Rh2(TFA)4 and Rh2(OAc)4, and as organic linker benzene 1,4-dicarboxylate (bdc) are employed. The successful synthesis of the Rh2-bdc(Tf) and Rh2-bdc(Ac) catalysts is proven by ATR-IR, XPS and 13C CP MAS NMR. Residual trifluoroacetate species are investigated by quantitative 19F MAS NMR which further reflects the configuration of trifluoroacetate in the obtained Rh2-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.

Item Type: Article
Erschienen: 2016
Creators: Liu, Jiquan and Fasel, Claudia and Braga-Groszewicz, Pedro and Rothermel, Niels and Lilly Thankamony, Aany Sofia and Sauer, Grit and Xu, Yeping and Gutmann, Torsten and Buntkowsky, Gerd
Title: Heterogeneous self-supported dirhodium(ii) catalysts with high catalytic efficiency in cyclopropanation – a structural study
Language: English
Abstract:

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 Rh2(TFA)4 and Rh2(OAc)4, and as organic linker benzene 1,4-dicarboxylate (bdc) are employed. The successful synthesis of the Rh2-bdc(Tf) and Rh2-bdc(Ac) catalysts is proven by ATR-IR, XPS and 13C CP MAS NMR. Residual trifluoroacetate species are investigated by quantitative 19F MAS NMR which further reflects the configuration of trifluoroacetate in the obtained Rh2-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.

Journal or Publication Title: Catal. Sci. Technol.
Volume: 6
Number: 21
Publisher: Royal Society of Chemistry
Divisions: 11 Department of Materials and Earth Sciences > Material Science > Dispersive Solids
07 Department of Chemistry
11 Department of Materials and Earth Sciences > Material Science
11 Department of Materials and Earth Sciences
Date Deposited: 25 Oct 2016 12:28
Official URL: http://dx.doi.org/10.1039/C6CY00915H
Identification Number: doi:10.1039/C6CY00915H
Funders: Financial support by the Deutsche Forschungsgemeinschaft DFG under contract Bu 911-22-1, and by the Hessen State Ministry of Higher Education, Research and the Arts in the frame of the LOEWE project iNAPO is gratefully acknowledged
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