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

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

doi:10.1021/jacs.9b09620

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

Journal Article · Fri Nov 29 00:00:00 EST 2019 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.9b09620· OSTI ID:2433867

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Texas A & M University, College Station, TX (United States); Texas A&M University
Texas A & M University, College Station, TX (United States)

The porosity and synthetic tunability of metalorganic frameworks (MOFs) motivate 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. Here, 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.

View Accepted Manuscript (DOE)

Research Organization:: Texas A & M University, College Station, TX (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); Welch Foundation

Grant/Contract Number:: SC0018977

OSTI ID:: 2433867

Alternate ID(s):: OSTI ID: 1803483

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 49 Vol. 141; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (26)

On the Interpretation of Deuterium Kinetic Isotope Effects in CH Bond Functionalizations by Transition-Metal Complexes Simmons, Eric M.; Hartwig, John F. Angewandte Chemie International Edition, Vol. 51, Issue 13 https://doi.org/10.1002/anie.201107334	journal	March 2012
Multifunctional, Defect-Engineered Metal-Organic Frameworks with Ruthenium Centers: Sorption and Catalytic Properties Kozachuk, Olesia; Luz, Ignacio; Llabrés i. Xamena, Francesc X. Angewandte Chemie International Edition, Vol. 53, Issue 27 https://doi.org/10.1002/anie.201311128	journal	May 2014
Probing Substrate Diffusion in Interstitial MOF Chemistry with Kinetic Isotope Effects Wang, Chen-Hao; Das, Anuvab; Gao, Wen-Yang Angewandte Chemie International Edition, Vol. 57, Issue 14 https://doi.org/10.1002/anie.201713244	journal	March 2018
A simple and practical protocol for the palladium-catalyzed cross-coupling of boronic acids with methyl iodide: Catalyzed cross-coupling of boronic acids with methyl iodide Gooßen, Lukas J. Applied Organometallic Chemistry, Vol. 18, Issue 11 https://doi.org/10.1002/aoc.746	journal	October 2004
Metal-Organic Frameworks as Biomimetic Catalysts Gu, Zhi-Yuan; Park, Jihye; Raiff, Aaron ChemCatChem, Vol. 6, Issue 1 https://doi.org/10.1002/cctc.201300493	journal	October 2013
Kinetic isotope effects and mechanism of biomimetic oxidation of methane and benzene on FeZSM-5 zeolite Dubkov, K. A.; Sobolev, V. I.; Talsi, E. P. Journal of Molecular Catalysis A: Chemical, Vol. 123, Issue 2-3 https://doi.org/10.1016/S1381-1169(97)00051-4	journal	August 1997
Mechanochemical synthesis of Cu-BTC@GO with enhanced water stability and toluene adsorption capacity Li, Yujie; Miao, Jinpeng; Sun, Xuejiao Chemical Engineering Journal, Vol. 298 https://doi.org/10.1016/j.cej.2016.03.141	journal	August 2016
Synthesis, structural properties, and catalytic behavior of Cu-BTC and mixed-linker Cu-BTC-PyDC in the oxidation of benzene derivatives Marx, Stefan; Kleist, Wolfgang; Baiker, Alfons Journal of Catalysis, Vol. 281, Issue 1 https://doi.org/10.1016/j.jcat.2011.04.004	journal	July 2011
Understanding Biological Hydrogen Transfer Through the Lens of Temperature Dependent Kinetic Isotope Effects Klinman, Judith P.; Offenbacher, Adam R. Accounts of Chemical Research, Vol. 51, Issue 9 https://doi.org/10.1021/acs.accounts.8b00226	journal	August 2018
Oxygen Activation and Radical Transformations in Heme Proteins and Metalloporphyrins Huang, Xiongyi; Groves, John T. Chemical Reviews, Vol. 118, Issue 5 https://doi.org/10.1021/acs.chemrev.7b00373	journal	December 2017
Catalysis by Metal Organic Frameworks: Perspective and Suggestions for Future Research Yang, Dong; Gates, Bruce C. ACS Catalysis, Vol. 9, Issue 3 https://doi.org/10.1021/acscatal.8b04515	journal	January 2019
Hydrocarbon Hydroxylation by Cytochrome P450 Enzymes Ortiz de Montellano, Paul R. Chemical Reviews, Vol. 110, Issue 2 https://doi.org/10.1021/cr9002193	journal	February 2010
Inter- and Intramolecular Experimental and Calculated Equilibrium Isotope Effects for (silox) ₂ ( ^t Bu ₃ SiND)TiR + RH (silox = ^t Bu ₃ SiO): Inferred Kinetic Isotope Effects for RH/D Addition to Transient (silox) ₂ TiNSi ^t Bu ₃ Slaughter, LeGrande M.; Wolczanski, Peter T.; Klinckman, Thomas R. Journal of the American Chemical Society, Vol. 122, Issue 33 https://doi.org/10.1021/ja000112q	journal	August 2000
The experimental manifestations of corner-cutting tunneling Kim, Yongho; Kreevoy, Maurice M. Journal of the American Chemical Society, Vol. 114, Issue 18 https://doi.org/10.1021/ja00044a024	journal	August 1992
Cryptic stereospecificity of methane monooxygenase Priestley, N. D.; Floss, H. G.; Froland, W. A. Journal of the American Chemical Society, Vol. 114, Issue 19 https://doi.org/10.1021/ja00045a037	journal	September 1992
Unmasking of Deuterium Kinetic Isotope Effects on the Methane Monooxygenase Compound Q Reaction by Site-Directed Mutagenesis of Component B Brazeau, Brian J.; Wallar, Bradley J.; Lipscomb, John D. Journal of the American Chemical Society, Vol. 123, Issue 42 https://doi.org/10.1021/ja016632i	journal	October 2001
Synthesis and Catalytic Properties of Metal Clusters Encapsulated within Small-Pore (SOD, GIS, ANA) Zeolites Goel, Sarika; Wu, Zhijie; Zones, Stacey I. Journal of the American Chemical Society, Vol. 134, Issue 42, p. 17688-17695 https://doi.org/10.1021/ja307370z	journal	October 2012
Structural Complexity in Metal–Organic Frameworks: Simultaneous Modification of Open Metal Sites and Hierarchical Porosity by Systematic Doping with Defective Linkers Fang, Zhenlan; Dürholt, Johannes P.; Kauer, Max Journal of the American Chemical Society, Vol. 136, Issue 27 https://doi.org/10.1021/ja503218j	journal	June 2014
Experimental Evidence for Extensive Tunneling of Hydrogen in the Lipoxygenase Reaction: Implications for Enzyme Catalysis Jonsson, Thorlakur; Glickman, Michael H.; Sun, Shujun Journal of the American Chemical Society, Vol. 118, Issue 42 https://doi.org/10.1021/ja961827p	journal	January 1996
Metal–Organic Frameworks as Catalysts for Organic Synthesis: A Critical Perspective Pascanu, Vlad; González Miera, Greco; Inge, A. Ken Journal of the American Chemical Society, Vol. 141, Issue 18 https://doi.org/10.1021/jacs.9b00733	journal	April 2019
Adsorption and Separation of Xylene Isomers: CPO-27-Ni vs HKUST-1 vs NaY Peralta, David; Barthelet, Karin; Pérez-Pellitero, Javier The Journal of Physical Chemistry C, Vol. 116, Issue 41 https://doi.org/10.1021/jp306828x	journal	October 2012
Metal organic frameworks mimicking natural enzymes: a structural and functional analogy Nath, Ipsita; Chakraborty, Jeet; Verpoort, Francis Chemical Society Reviews, Vol. 45, Issue 15 https://doi.org/10.1039/C6CS00047A	journal	January 2016
Metal–organic and covalent organic frameworks as single-site catalysts Rogge, S. M. J.; Bavykina, A.; Hajek, J. Chemical Society Reviews, Vol. 46, Issue 11 https://doi.org/10.1039/C7CS00033B	journal	January 2017
Metal–organic framework materials as catalysts Lee, JeongYong; Farha, Omar K.; Roberts, John Chemical Society Reviews, Vol. 38, Issue 5, p. 1450-1459 https://doi.org/10.1039/b807080f	journal	January 2009
Diffusion in porous crystalline materials Krishna, Rajamani Chemical Society Reviews, Vol. 41, Issue 8 https://doi.org/10.1039/c2cs15284c	journal	January 2012
A Perspective on Enzyme Catalysis Benkovic, S. J. Science, Vol. 301, Issue 5637 https://doi.org/10.1126/science.1085515	journal	August 2003

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