Probing substrate diffusion in interstitial MOF chemistry with kinetic isotope effects Conference Paper uri icon

abstract

  • AbstractMetalorganic frameworks (MOFs) have garnered substantial interest as platforms for siteisolated catalysis. Efficient diffusion of smallmolecule substrates to interstitial latticeconfined 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 insitu chemical tools are available to evaluate substrate diffusion during interstitial MOF chemistry. Herein, we demonstrate nitrogen atom transfer (NAT) from a latticeconfined 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 KIEbased experiments will contribute to the development of porous materials for grouptransfer catalysis.

published proceedings

  • ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY

author list (cited authors)

  • Powers, D.

citation count

  • 12

complete list of authors

  • Powers, David

publication date

  • March 2019

publisher