Change search
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf
Synthesis of Benzofurans and Indoles from Terminal Alkynes and Iodoaromatics Catalyzed by Recyclable Palladium Nanoparticles Immobilized on Siliceous Mesocellular Foam
Stockholm University, Faculty of Science, Department of Organic Chemistry.
Stockholm University, Faculty of Science, Department of Organic Chemistry.
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK). Swedish University of Agricultural Sciences, Sweden.
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
Show others and affiliations
2017 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 23, no 52, p. 12886-12891Article in journal (Refereed) Published
Abstract [en]

Herein, we report on the utilization of a heterogeneous catalyst, consisting of Pd nanoparticles supported on a siliceous mesocellular foam (Pd-0-AmP-MCF), for the synthesis of heterocycles. Reaction of o-iodophenols and protected o-iodoanilines with acetylenes in the presence of a Pd nanocatalyst produced 2-substituted benzofurans and indoles, respectively. In general, the catalytic protocol afforded the desired products in good to excellent yields under mild reaction conditions without the addition of ligands. Moreover, the structure of the reported Pd nanocatalyst was further elucidated with extended X-ray absorption fine-structure spectroscopy, and it was proven that the catalyst could be recycled multiple times without significant loss of activity.

Place, publisher, year, edition, pages
2017. Vol. 23, no 52, p. 12886-12891
Keywords [en]
benzofurans, extended x-ray absorption fine structure, heterogeneous catalysis, indoles, palladium
National Category
Chemical Sciences
Research subject
Inorganic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-148090DOI: 10.1002/chem.201702614ISI: 000411033800029PubMedID: 28736879OAI: oai:DiVA.org:su-148090DiVA, id: diva2:1150873
Funder
Swedish Research CouncilBerzelii Centre EXSELENTEU, European Research CouncilKnut and Alice Wallenberg FoundationAvailable from: 2017-10-20 Created: 2017-10-20 Last updated: 2019-03-29Bibliographically approved
In thesis
1. Unveiling Catalytic Species in Suspension/Solution-Based Reactions by In Situ X-Ray Absorption Spectroscopy: Evolution of Palladium and Ruthenium Species
Open this publication in new window or tab >>Unveiling Catalytic Species in Suspension/Solution-Based Reactions by In Situ X-Ray Absorption Spectroscopy: Evolution of Palladium and Ruthenium Species
2019 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The palladium (Pd) and ruthenium (Ru) species in several attractive catalysts have been probed using X-ray absorption spectroscopy (XAS). The study of catalyst evolution in suspension- and solution-based reactions was the primary aim. It was achieved by performing in situ XAS experiments on Pd and Ru over the course of the reactions. A custom-made reactor was employed which allowed the catalysts to be mixed with other reaction components under desired conditions.

The first system investigated was the Heck coupling reaction catalyzed by Pd(II) complexes embedded on metal-organic frameworks. It was realized that the as-synthesized catalysts go through an instant ligand substitution process when added to the reaction mixture. Mononuclear Pd complexes are the active species at the first stage of the measurement which then gradually transform into Pd nanoclusters. At a later stage of the measurement, chloride ligands start to bind to surface atoms of the Pd nanoclusters, leading to a deactivation of the catalyst. Following the first successful in situ XAS experiment, Pd(II) carbene complexes catalyzing undirected C–H acetoxylation of benzene in the presence of an oxidant were explored. A gradual ligand substitution occurs, and the mean oxidation state of Pd increases at the same time. At a later stage, Pd nanoclusters form, while the mean oxidation state of Pd returns to the start value. Deactivation of a heterogeneous Pd(II) catalyst during cycloisomerization of acetylenic acids was then investigated using in situ XAS. The choice of substrates showed to significantly influence the nature of Pd species, and the reduction of Pd(II) forming Pd(0) aggregates causes the deactivation. Moreover, strategies of reactivating the catalyst and prevention of the deactivation were developed and examined. In the end, the activation process of a Ru catalyst was studied and the structure of the intermediate was determined by in situ XAS. It was demonstrated that an electron-donating substituent on the cyclopentadiene ligand exhibits a promoting effect on the activation, while an electron-withdrawing substituent inhibits the activation.

Place, publisher, year, edition, pages
Stockholm: Department of Materials and Environmental Chemistry (MMK), Stockholm University, 2019. p. 112
Keywords
Palladium and ruthenium species, Catalysts, Suspension and solution, In situ X-ray absorption spectroscopy, Activation, Deactivation
National Category
Inorganic Chemistry
Research subject
Inorganic Chemistry
Identifiers
urn:nbn:se:su:diva-167340 (URN)978-91-7797-578-6 (ISBN)978-91-7797-579-3 (ISBN)
Public defence
2019-05-21, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 13:00 (English)
Opponent
Supervisors
Note

At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 3: Manuscript. Paper 5: Manuscript. Paper 6: Manuscript.

Available from: 2019-04-25 Created: 2019-03-26 Last updated: 2019-04-12Bibliographically approved

Open Access in DiVA

fulltext(954 kB)25 downloads
File information
File name FULLTEXT01.pdfFile size 954 kBChecksum SHA-512
e0a45fdd73591529fcce77b3de624ea237ef40681e3768af3e1ed568122bb513e941c1122ec8325c0fb2930c19c73ab611f46a1aed79a5bb22a03540cf88c3eb
Type fulltextMimetype application/pdf

Other links

Publisher's full textPubMed

Search in DiVA

By author/editor
Gustafson, Karl P. J.Yuan, NingTai, Cheuk-WaiZou, XiaodongBäckvall, Jan-E.
By organisation
Department of Organic ChemistryDepartment of Materials and Environmental Chemistry (MMK)
In the same journal
Chemistry - A European Journal
Chemical Sciences

Search outside of DiVA

GoogleGoogle Scholar
Total: 25 downloads
The number of downloads is the sum of all downloads of full texts. It may include eg previous versions that are now no longer available

doi
pubmed
urn-nbn

Altmetric score

doi
pubmed
urn-nbn
Total: 59 hits
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf