Probing Substrate Diffusion in Interstitial MOF Chemistry with Kinetic Isotope Effects

Metal–organic frameworks (MOFs) have garnered substantial interest as platforms for site‐isolated catalysis. Efficient diffusion of small‐molecule substrates to interstitial lattice‐confined catalyst sites is critical to leveraging unique opportunities of these materials as catalysts. Understanding...

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Bibliographic Details
Published inAngewandte Chemie Vol. 130; no. 14; pp. 3738 - 3743
Main Authors Wang, Chen‐Hao, Das, Anuvab, Gao, Wen‐Yang, Powers, David C.
Format Journal Article
LanguageEnglish
German
Published Weinheim Wiley Subscription Services, Inc 26.03.2018
Subjects
Amination
C-H-Funktionalisierung
Catalysis
Catalysts
Chemistry
Deuteration
Deuterium
Diffusion
Diffusion rate
Heterogene Katalyse
Isotope effect
Kinetische Isotopeneffekte
Metal-organic frameworks
Porous materials
Poröse Materialien
Substrates
Toluene
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Summary:Metal–organic frameworks (MOFs) have garnered substantial interest as platforms for site‐isolated catalysis. Efficient diffusion of small‐molecule substrates to interstitial lattice‐confined catalyst sites is critical to leveraging unique opportunities of these materials as catalysts. Understanding the rates of substrate diffusion in MOFs is challenging, and few in situ chemical tools are available to evaluate substrate diffusion during interstitial MOF chemistry. Herein, we demonstrate nitrogen atom transfer (NAT) from a lattice‐confined Ru2 nitride to toluene to generate benzylamine. We use the comparison of the intramolecular deuterium kinetic isotope effect (KIE), determined for amination of a partially deuterated substrate, with the intermolecular KIE, determined by competitive amination of a mixture of perdeuterated and undeuterated substrates, to establish the relative rates of substrate diffusion and interstitial chemistry. We anticipate that the developed KIE‐based experiments will contribute to the development of porous materials for group‐transfer catalysis. Stickstoffatomtransfer von einem gittergebundenen Ru2‐Nitrid zu Toluol ergibt Benzylamin. Der mit einem teilweise deuterierten Substrat bestimmte intramolekulare kinetische Isotopeneffekt (KIE) wurde mit dem intermolekularen KIE, der durch die Aminierung einer Mischung aus perdeuteriertem und nicht deuteriertem Substrat berechnet wurde, verglichen, um die relativen Geschwindigkeiten der Substratdiffusion und der interstitiellen Reaktion zu erhalten.
ISSN:0044-8249
1521-3757
DOI:10.1002/ange.201713244