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Title
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S,O-functionalized metal-organic frameworks as heterogeneous single-site catalysts for the oxidative alkenylation of arenes via C- H activation
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Author
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Abstract
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| Heterogeneous single-site catalysts can combine the R precise active site design of organometallic complexes with the efficient recovery of solid catalysts. Based on recent progress on homogeneous thioether ligands for Pd-catalyzed C-H activation reactions, we here develop a scalable metal-organic framework-based heterogeneous single-site catalyst containing S,O-moieties that increase the catalytic activity of Pd(II) for the oxidative alkenylation of arenes. The structure of the Pd@MOF-808-L1 catalyst was characterized in detail via solid-state nuclear magnetic resonance spectroscopy, N-2 physisorption, and high-angle annular dark field scanning transmission electron microscopy, and the structure of the isolated palladium active sites could be identified by X-ray absorption spectroscopy. A turnover frequency (TOF) of 8.4 h(-1) was reached after 1 h of reaction time, which was 3 times higher than the TOF of standard Pd(OAc)(2), ranking Pd@MOF-808-L1 among the most active heterogeneous catalysts ever reported for the nondirected oxidative alkenylation of arenes. Finally, we showed that the single-site catalyst promotes the oxidative alkenylation of a broad range of electron-rich arenes, and the applicability of this heterogeneous system was demonstrated by the gram-scale synthesis of industrially relevant products. |
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Language
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English
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Source (journal)
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ACS catalysis. - -
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Publication
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2020
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ISSN
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2155-5435
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DOI
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10.1021/ACSCATAL.0C00801
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Volume/pages
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10
:9
(2020)
, p. 5077-5085
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ISI
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000530090800026
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Full text (Publisher's DOI)
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Full text (open access)
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Full text (publisher's version - intranet only)
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