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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Published in | Angewandte Chemie (International ed.) Vol. 57; no. 14; pp. 3676 - 3681 |
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Main Authors | , , , |
Format | Journal Article |
Language | English |
Published |
Germany
Wiley Subscription Services, Inc
26.03.2018
Wiley |
Edition | International ed. in English |
Subjects | |
Online Access | Get full text |
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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.
Nitrogen atom transfer from a lattice‐confined Ru2 nitride to toluene generates benzylamine. The intramolecular deuterium kinetic isotope effect (KIE), determined for the amination of a partially deuterated substrate, was compared with the intermolecular KIE, determined by competitive amination of a mixture of perdeuterated and nondeuterated substrate, to establish the relative rates of substrate diffusion and interstitial chemistry. |
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Bibliography: | ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23 AC02- 06CH11357 USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division |
ISSN: | 1433-7851 1521-3773 |
DOI: | 10.1002/anie.201713244 |