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Selective Heterogeneous C−H Activation/Halogenation Reactions Catalyzed by Pd@MOF Nanocomposites
Stockholm University, Faculty of Science, Department of Organic Chemistry.
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
Stockholm University, Faculty of Science, Department of Organic Chemistry.
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
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2016 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 22, no 11, 3729-3737 p.Article in journal (Refereed) Published
Abstract [en]

A directed heterogeneous C−H activation/halogenation reaction catalyzed by readily synthesized Pd@MOF nanocatalysts was developed. The heterogeneous Pd catalysts used were a novel and environmentally benign Fe-based metal–organic framework (MOF) (Pd@MIL-88B-NH2(Fe)) and the previously developed Pd@MIL-101-NH2(Cr). Very high conversions and selectivities were achieved under very mild reaction conditions and in short reaction times. A wide variety of directing groups, halogen sources, and substitution patterns were well tolerated, and valuable polyhalogenated compounds were synthesized in a controlled manner. The synthesis of the Pd-functionalized Fe-based MOF and the recyclability of the two catalysts are also presented.

Place, publisher, year, edition, pages
2016. Vol. 22, no 11, 3729-3737 p.
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-132704DOI: 10.1002/chem.201502918ISI: 000371741400027PubMedID: 26481867OAI: oai:DiVA.org:su-132704DiVA: diva2:953873
Available from: 2016-08-19 Created: 2016-08-19 Last updated: 2016-08-26Bibliographically approved
In thesis
1. Catalytic Processes Mediated by Metal−Organic Frameworks: Reactivity and Mechanistic Studies
Open this publication in new window or tab >>Catalytic Processes Mediated by Metal−Organic Frameworks: Reactivity and Mechanistic Studies
2016 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The present thesis describes the development of heterogeneous catalytic methodologies using metal−organic frameworks (MOFs) as porous matrices for supporting transition metal catalysts. A wide spectrum of chemical reactions is covered. Following the introductory section (Chapter 1), the results are divided between one descriptive part (Chapter 2) and four experimental parts (Chapters 3–6).

Chapter 2 provides a detailed account of MOFs and their role in heterogeneous catalysis. Specific synthesis methods and characterization techniques that may be unfamiliar to organic chemists are illustrated based on examples from this work.

Pd-catalyzed heterogeneous C−C coupling and C−H functionalization reactions are studied in Chapter 3, with focus on their practical utility. A vast functional group tolerance is reported, allowing access to substrates of relevance for the pharmaceutical industry. Issues concerning the recyclability of MOF-supported catalysts, leaching and operation under continuous flow are discussed in detail.

The following chapter explores puzzling questions regarding the nature of the catalytically active species and the pathways of deactivation for Pd@MOF catalysts. These questions are addressed through detailed mechanistic investigations which include in situ XRD and XAS data acquisition. For this purpose a custom reaction cell is also described in Chapter 4.

The scope of Pd@MOF-catalyzed reactions is expanded in Chapter 5. A strategy for boosting the thermal and chemical robustness of MOF crystals is presented. Pd@MOF catalysts are coated with a protecting SiO2 layer, which improves their mechanical properties without impeding diffusion. The resulting nanocomposite is better suited to withstand the harsh conditions of aerobic oxidation reactions. In this chapter, the influence of the nanoparticles’ geometry over the catalyst’s selectivity is also investigated.

While Chapters 3–5 dealt with Pd-catalyzed processes, Chapter 6 introduces hybrid materials based on first-row transition metals. Their reactivity is explored towards light-driven water splitting. The heterogenization process leads to stabilized active sites, facilitating the spectroscopic probing of intermediates in the catalytic cycle.

Place, publisher, year, edition, pages
Stockholm: Department of Organic Chemistry, Stockholm University, 2016. 122 p.
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-132711 (URN)978-91-7649-485-1 (ISBN)
External cooperation:
Public defence
2016-10-07, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 10:00 (English)
Opponent
Supervisors
Note

At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 5: Submitted. Paper 8: Submitted.

 

Available from: 2016-09-14 Created: 2016-08-19 Last updated: 2016-09-02Bibliographically approved

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Pascanu, VladVico Solano, MartaSu, JieZou, XiaodongMartín-Matute, Belén
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