Measuring and Modulating Substrate Confinement during Nitrogen-Atom Transfer in a Ru₂-Based Metal-Organic Framework

The porosity and synthetic tunability of metal-organic frameworks (MOFs) has motivated interest in application of these materials as designer heterogeneous catalysts. While understanding substrate mobility in these materials is critical to the rational development of highly active catalyst platforms, experimental data are rarely available. Here we demonstrate kinetic isotope effect (KIE) analysis enables direct evaluation of the extent of substrate confinement as a function of material mesoporosity. Further, we provide evidence that suggests substrate confinement within a microporous Ru₂-based MOF gives rise to quantum tunneling during interstitial C-H amination. The reported data provide the first evidence for tunneling during interstitial MOF chemistry and illustrate an experimental strategy to evaluate the impact of material structure on substrate mobility in porous catalysts.