Probing Substrate Diffusion in Interstitial MOF Chemistry with Kinetic Isotope Effects

Wang, Chen-Hao; Das, Anuvab; Gao, Wen-Yang; Powers, David C.

doi:10.1002/anie.201713244

Probing Substrate Diffusion in Interstitial MOF Chemistry with Kinetic Isotope Effects

Journal Article · Fri Feb 09 00:00:00 EST 2018 · Angewandte Chemie (International Edition)

DOI:https://doi.org/10.1002/anie.201713244· OSTI ID:1433707

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Texas A & M Univ., College Station, TX (United States)

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.

View Accepted Manuscript (DOE)

Research Organization:: Advanced Photon Source (APS), Argonne National Laboratory (ANL), Argonne, IL (US)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1433707

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 14 Vol. 57; ISSN 1433-7851

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: ENGLISH

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