On the mechanism of intermolecular nitrogen-atom transfer from a lattice-isolated diruthenium nitride intermediate

Cosio, Mario N; Alharbi, Waad S.; Sur, Aishanee; Wang, Chen-Hao; Najafian, Ahmad; Cundari, Thomas R.; Powers, David C.

doi:10.1039/d2fd00167e

On the mechanism of intermolecular nitrogen-atom transfer from a lattice-isolated diruthenium nitride intermediate

Journal Article · Thu Dec 22 00:00:00 EST 2022 · Faraday Discussions

DOI:https://doi.org/10.1039/d2fd00167e· OSTI ID:1909455

Cosio, Mario N ^[1]; ^[2]; Sur, Aishanee ^[3]; Wang, Chen-Hao ^[3]; Najafian, Ahmad ^[4]; Cundari, Thomas R. ^[4]; ^[3]

Texas A & M Univ., College Station, TX (United States); Univ. North Texas
Univ. of North Texas, Denton, TX (United States). Center for Advanced Scientific Computing and Modeling (CASCaM); University of Jeddah (Saudi Arabia)
Texas A & M Univ., College Station, TX (United States)
Univ. of North Texas, Denton, TX (United States). Center for Advanced Scientific Computing and Modeling (CASCaM)

Catalyst confinement within microporous media provides the opportunity to site isolate reactive intermediates, enforce intermolecular functionalization chemistry by co-localizing reactive intermediates and substrates in molecular-scale interstices, and harness non-covalent host–guest interactions to achieve selectivities that are complementary to those accessible in solution. As part of an ongoing program to develop synthetically useful nitrogen-atom transfer (NAT) catalysts, we have demonstrated intermolecular benzylic amination of toluene at a Ru₂ nitride intermediate confined within the interstices of a Ru2-based metal–organic framework (MOF), Ru₃(btc)₂X₃ (btc = 1,3,5-benzenetricarboxylate, i.e., Ru-HKUST-1 for X = Cl). Nitride confinement within the extended MOF lattice enabled intermolecular C–H functionalization of benzylic C–H bonds in preference to nitride dimerization, which was encountered with soluble molecular analogues. Detailed study of the kinetic isotope effects (KIEs, i.e., k_H/k_D) of C–H amination, assayed both as intramolecular effects using partially labeled toluene and as intermolecular effects using a mixture of per-labeled and unlabeled toluene, provided evidence for restricted substrate mobility on the time scale of interstitial NAT. Analysis of these KIEs as a function of material mesoporosity provided approximate experimental values for functionalization in the absence of mass transport barriers. Here, we disclose a combined experimental and computational investigation of the mechanism of NAT from a Ru₂ nitride to the C–H bond of toluene. Computed kinetic isotope effects for a H-atom abstraction (HAA)/radical rebound (RR) mechanism are in good agreement with experimental data obtained for C–H amination at the rapid diffusion limit. These results provide the first detailed analysis of the mechanism of intermolecular NAT to a C–H bond, bolster the use of KIEs as a probe of confinement effects on NAT within MOF lattices, and provide mechanistic insights unavailable by experiment because rate-determining mass transport obscured the underlying chemical kinetics.

View Accepted Manuscript (DOE)

Research Organization:: Texas A & M University, College Station, TX (United States); Univ. of North Texas, Denton, TX (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: FG02-03ER15387; SC0018977

OSTI ID:: 1909455

Alternate ID(s):: OSTI ID: 2433864
OSTI ID: 1971537

Journal Information:: Faraday Discussions, Journal Name: Faraday Discussions Vol. 244; ISSN 1359-6640

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

References (55)

Diffusion in a pore of varying cross section Petersen, E. E. AIChE Journal, Vol. 4, Issue 3 https://doi.org/10.1002/aic.690040322	journal	September 1958
Unusual Reaction Pathways in the Photolysis of Diazido(phosphane)nickel(II) Complexes: Nitrenes As Intermediates in the Formation of Nickel(0) Complexes Henning, Horst; Hofbauer, Katrin; Handke, Kartin Angewandte Chemie International Edition in English, Vol. 36, Issue 4 https://doi.org/10.1002/anie.199704081	journal	March 1997
Delocalized Metal-Metal and Metal-Ligand Multiple Bonding in a Linear RuRuN Unit: Elongation of a Traditionally Short RuN Bond Pap, József S.; DeBeer George, Serena; Berry, John F. Angewandte Chemie International Edition, Vol. 47, Issue 52 https://doi.org/10.1002/anie.200804397	journal	December 2008
Ligand-Accelerated Activation of Strong CH Bonds of Alkanes by a (Salen)ruthenium(VI)-Nitrido Complex Man, Wai-Lun; Lam, William W. Y.; Kwong, Hoi-Ki Angewandte Chemie International Edition, Vol. 51, Issue 36 https://doi.org/10.1002/anie.201204136	journal	July 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
Decay of Iron(V) Nitride Complexes By a NN Bond-Coupling Reaction in Solution: A Combined Spectroscopic and Theoretical Analysis Krahe, Oliver; Bill, Eckhard; Neese, Frank Angewandte Chemie International Edition, Vol. 53, Issue 33 https://doi.org/10.1002/anie.201403402	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
Traceless Benzylic C−H Amination via Bifunctional N ‐Aminopyridinium Intermediates Roychowdhury, Pritam; Herrera, Roberto G.; Tan, Hao Angewandte Chemie International Edition, Vol. 61, Issue 28 https://doi.org/10.1002/anie.202200665	journal	May 2022
Ruthenium Metal-Organic Frameworks with Different Defect Types: Influence on Porosity, Sorption, and Catalytic Properties Zhang, Wenhua; Kauer, Max; Halbherr, Olesia Chemistry - A European Journal, Vol. 22, Issue 40 https://doi.org/10.1002/chem.201602641	journal	August 2016
In Operando Analysis of Diffusion in Porous Metal‐Organic Framework Catalysts Gao, Wen‐Yang; Cardenal, Ashley D.; Wang, Chen‐Hao Chemistry – A European Journal, Vol. 25, Issue 14 https://doi.org/10.1002/chem.201804490	journal	December 2018
Precise Control of Molecular Self‐Diffusion in Isoreticular and Multivariate Metal‐Organic Frameworks Osborn Popp, Thomas M.; Plantz, Ariel Z.; Yaghi, Omar M. ChemPhysChem, Vol. 21, Issue 1 https://doi.org/10.1002/cphc.201901043	journal	December 2019
4d vs. 5d – Reactivity and Fate of Terminal Nitrido Complexes of Rhodium and Iridium Schöffel, Julia; Šušnjar, Nevena; Nückel, Stefan European Journal of Inorganic Chemistry, Vol. 2010, Issue 31 https://doi.org/10.1002/ejic.201000899	journal	September 2010
Beyond ferryl-mediated hydroxylation: 40 years of the rebound mechanism and C–H activation Huang, Xiongyi; Groves, John T. JBIC Journal of Biological Inorganic Chemistry, Vol. 22, Issue 2-3 https://doi.org/10.1007/s00775-016-1414-3	journal	December 2016
The effect of dead-end porosity on rock-matrix diffusion Lever, D. A.; Bradbury, M. H.; Hemingway, S. J. Journal of Hydrology, Vol. 80, Issue 1-2 https://doi.org/10.1016/0022-1694(85)90074-5	journal	September 1985
Immobilizing catalysts on porous materials Zhao, X. S.; Bao, Xiao Ying; Guo, Wanping Materials Today, Vol. 9, Issue 3, p. 32-39 https://doi.org/10.1016/S1369-7021(06)71388-8	journal	March 2006
Immobilized highly dispersed Ni nanoparticles over porous carbon as an efficient catalyst for selective hydrogenation of furfural and levulinic acid Balla, Putrakumar; Seelam, Prem Kumar; Balaga, Ravi Journal of Environmental Chemical Engineering, Vol. 9, Issue 6 https://doi.org/10.1016/j.jece.2021.106530	journal	December 2021
Transition-Metal-Catalyzed C–N Bond Forming Reactions Using Organic Azides as the Nitrogen Source: A Journey for the Mild and Versatile C–H Amination Shin, Kwangmin; Kim, Hyunwoo; Chang, Sukbok Accounts of Chemical Research, Vol. 48, Issue 4 https://doi.org/10.1021/acs.accounts.5b00020	journal	March 2015
Elucidating the Structure of the Metal–Organic Framework Ru-HKUST-1 Lorzing, Gregory R.; Balto, Krista P.; Antonio, Alexandra M. Chemistry of Materials, Vol. 32, Issue 18 https://doi.org/10.1021/acs.chemmater.0c01944	journal	August 2020
Reusable N-Heterocyclic Carbene Complex Catalysts and Beyond: A Perspective on Recycling Strategies Wang, Wenlong; Cui, Lifeng; Sun, Peng Chemical Reviews, Vol. 118, Issue 19 https://doi.org/10.1021/acs.chemrev.8b00057	journal	May 2018
Diffusive Transport in Pores. Tortuosity and Molecular Interaction with the Pore Wall Elwinger, Fredrik; Pourmand, Payam; Furó, István The Journal of Physical Chemistry C, Vol. 121, Issue 25 https://doi.org/10.1021/acs.jpcc.7b03885	journal	June 2017
Recent Advances in Porous Materials for Photocatalytic CO₂ Reduction Xiong, Hailong; Dong, Yueyue; Liu, Dong The Journal of Physical Chemistry Letters, Vol. 13, Issue 5 https://doi.org/10.1021/acs.jpclett.1c03204	journal	January 2022
Post-Transition State Bifurcation in Iron-Catalyzed Arene Aminations Li, Bo; Li, Yuli; Dang, Yanfeng ACS Catalysis, Vol. 11, Issue 12 https://doi.org/10.1021/acscatal.1c01291	journal	May 2021
Exploiting Confinement Effects to Tune Selectivity in Cyclooctane Metathesis Pump, Eva; Cao, Zhen; Samantaray, Manoja K. ACS Catalysis, Vol. 7, Issue 10 https://doi.org/10.1021/acscatal.7b01249	journal	August 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
Metalloporphyrin Catalyzed C–H Amination Singh, Ritesh; Mukherjee, Anirban ACS Catalysis, Vol. 9, Issue 4 https://doi.org/10.1021/acscatal.9b00009	journal	March 2019
Metal-Catalyzed Nitrogen-Atom Transfer Methods for the Oxidation of Aliphatic C–H Bonds Roizen, Jennifer L.; Harvey, Mark Edwin; Du Bois, J. Accounts of Chemical Research, Vol. 45, Issue 6 https://doi.org/10.1021/ar200318q	journal	January 2012
Acceleration and selectivity enhancement of Diels-Alder reactions by special and catalytic methods Pindur, Ulf.; Lutz, Gundula.; Otto, Christian. Chemical Reviews, Vol. 93, Issue 2 https://doi.org/10.1021/cr00018a006	journal	March 1993
Mesostructured Hybrid Organic–Silica Materials: Ideal Supports for Well-Defined Heterogeneous Organometallic Catalysts Conley, Matthew P.; Copéret, Christophe; Thieuleux, Chloé ACS Catalysis, Vol. 4, Issue 5 https://doi.org/10.1021/cs500262t	journal	April 2014
Localization in trans,trans -[(tpy)(Cl) ₂ Os ^III (N ₂ )Os ^II (Cl) ₂ (tpy)] ⁺ (tpy = 2,2‘:6‘,2‘‘-Terpyridine) Demadis, Konstantinos D.; Meyer, Thomas J.; White, Peter S. Inorganic Chemistry, Vol. 36, Issue 25 https://doi.org/10.1021/ic970885o	journal	December 1997
Adsorption of Branched and Cyclic Paraffins in Silicalite. 2. Kinetics Cavalcante, Celio L. Jr.; Ruthven, Douglas M. Industrial & Engineering Chemistry Research, Vol. 34, Issue 1 https://doi.org/10.1021/ie00040a018	journal	January 1995
Relation between Catalytic Activity and Size of Particle Thiele, E. W. Industrial & Engineering Chemistry, Vol. 31, Issue 7 https://doi.org/10.1021/ie50355a027	journal	July 1939
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
Highly Electrophilic (Salen)ruthenium(VI) Nitrido Complexes Man, Wai-Lun; Tang, Tsz-Man; Wong, Tsz-Wing Journal of the American Chemical Society, Vol. 126, Issue 2 https://doi.org/10.1021/ja037899f	journal	January 2004
Aryl C−H Bond Amination by an Electrophilic Diruthenium Nitride Musch Long, Amanda Kae; Yu, Renyuan Pony; Timmer, George H. Journal of the American Chemical Society, Vol. 132, Issue 35 https://doi.org/10.1021/ja1062955	journal	September 2010
Photolysis and Thermolysis of Bis(imino)pyridine Cobalt Azides: C−H Activation from Putative Cobalt Nitrido Complexes Hojilla Atienza, Crisita Carmen; Bowman, Amanda C.; Lobkovsky, Emil Journal of the American Chemical Society, Vol. 132, Issue 46 https://doi.org/10.1021/ja107288x	journal	November 2010
Electrophilic Aromatic Sulfonation with SO₃: Concerted or Classic S_EAr Mechanism? Koleva, Gergana; Galabov, Boris; Kong, Jing Journal of the American Chemical Society, Vol. 133, Issue 47 https://doi.org/10.1021/ja201866h	journal	November 2011
Aryl C–H Amination by Diruthenium Nitrides in the Solid State and in Solution at Room Temperature: Experimental and Computational Study of the Reaction Mechanism Long, Amanda Kae Musch; Timmer, George H.; Pap, József S. Journal of the American Chemical Society, Vol. 133, Issue 33 https://doi.org/10.1021/ja203993p	journal	August 2011
A Concerted Mechanism for Ethane Hydroxylation by the Particulate Methane Monooxygenase from Methylococcus capsulatus (Bath) Wilkinson, Barrie; Zhu, Mei; Priestley, Nigel D. Journal of the American Chemical Society, Vol. 118, Issue 4 https://doi.org/10.1021/ja953407q	journal	January 1996
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
Transport Phenomena: Challenges and Opportunities for Molecular Catalysis in Metal–Organic Frameworks Johnson, Ben A.; Beiler, Anna M.; McCarthy, Brian D. Journal of the American Chemical Society, Vol. 142, Issue 28 https://doi.org/10.1021/jacs.0c02899	journal	June 2020
Formation of the N≡N Triple Bond from Reductive Coupling of a Paramagnetic Diruthenium Nitrido Compound Park, Sungho V.; Corcos, Amanda R.; Jambor, Alexander N. Journal of the American Chemical Society, Vol. 144, Issue 7 https://doi.org/10.1021/jacs.1c13396	journal	February 2022
Four-Electron Oxidation of Phenols to p -Benzoquinone Imines by a (Salen)ruthenium(VI) Nitrido Complex Xie, Jianhui; Man, Wai-Lun; Wong, Chun-Yuen Journal of the American Chemical Society, Vol. 138, Issue 18 https://doi.org/10.1021/jacs.6b02923	journal	April 2016
Measuring and Modulating Substrate Confinement during Nitrogen-Atom Transfer in a Ru ₂ -Based Metal-Organic Framework Wang, Chen-Hao; Gao, Wen-Yang; Powers, David C. Journal of the American Chemical Society, Vol. 141, Issue 49 https://doi.org/10.1021/jacs.9b09620	journal	November 2019
N-Aminopyridinium reagents as traceless activating groups in the synthesis of N-Aryl aziridines Tan, Hao; Samanta, Samya; Maity, Asim Nature Communications, Vol. 13, Issue 1 https://doi.org/10.1038/s41467-022-31032-w	journal	June 2022
Manganese-catalysed benzylic C(sp3)–H amination for late-stage functionalization Clark, Joseph R.; Feng, Kaibo; Sookezian, Anasheh Nature Chemistry, Vol. 10, Issue 6 https://doi.org/10.1038/s41557-018-0020-0	journal	April 2018
Photochemical nitrogenation of alkanes and arenes by a strongly luminescent osmium(VI) nitrido complex Xiang, Jing; Jin, Xin-Xin; Su, Qian-Qian Communications Chemistry, Vol. 2, Issue 1 https://doi.org/10.1038/s42004-019-0142-3	journal	March 2019
Catalytic C–H functionalization by metalloporphyrins: recent developments and future directions Lu, Hongjian; Zhang, X. Peter Chem. Soc. Rev., Vol. 40, Issue 4 https://doi.org/10.1039/C0CS00070A	journal	January 2011
Immobilized Grubbs catalysts on mesoporous silica materials: insight into support characteristics and their impact on catalytic activity and product selectivity Dewaele, Annelies; Van Berlo, Boris; Dijkmans, Jan Catalysis Science & Technology, Vol. 6, Issue 8 https://doi.org/10.1039/C5CY01897H	journal	January 2016
Major advances in the development of ordered mesoporous materials Szczęśniak, Barbara; Choma, Jerzy; Jaroniec, Mietek Chemical Communications, Vol. 56, Issue 57 https://doi.org/10.1039/D0CC02840A	journal	January 2020
MOF-enabled confinement and related effects for chemical catalyst presentation and utilization Liu, Jian; Goetjen, Timothy A.; Wang, Qining Chemical Society Reviews, Vol. 51, Issue 3 https://doi.org/10.1039/D1CS00968K	journal	January 2022
Photoredox properties of [OsN(NH3)4]3+ and mechanism of formation of [{Os(NH3)4(CH3CN)}2N2]5+ through a nitrido-coupling reaction Lam, Hon-Wah; Che, Chi-Ming; Wong, Kwok-Yin Journal of the Chemical Society, Dalton Transactions, Issue 8 https://doi.org/10.1039/DT9920001411	journal	January 1992
Solvothermal growth of a ruthenium metal–organic framework featuring HKUST-1 structure type as thin films on oxide surfaces Kozachuk, Olesia; Yusenko, Kirill; Noei, Heshmat Chemical Communications, Vol. 47, Issue 30 https://doi.org/10.1039/c1cc11107h	journal	January 2011
Investigation of the synthesis, activation, and isosteric heats of CO2 adsorption of the isostructural series of metal–organic frameworks M3(BTC)2 (M = Cr, Fe, Ni, Cu, Mo, Ru) Wade, Casey R.; Dincă, Mircea Dalton Transactions, Vol. 41, Issue 26 https://doi.org/10.1039/c2dt30372h	journal	January 2012
N-Amino pyridinium salts in organic synthesis Roychowdhury, Pritam; Samanta, Samya; Tan, Hao Organic Chemistry Frontiers https://doi.org/10.1039/d3qo00190c	journal	January 2023
Stabilizing reactive intermediates through site isolation Copéret, Christophe Pure and Applied Chemistry, Vol. 81, Issue 4 https://doi.org/10.1351/PAC-CON-08-07-18	journal	January 2009

Similar Records

Probing Substrate Diffusion in Interstitial MOF Chemistry with Kinetic Isotope Effects

Journal Article · Thu Feb 08 19:00:00 EST 2018 · Angewandte Chemie (International Edition) · OSTI ID:1433707

Phenanthroline-based metal–organic frameworks for Fe-catalyzed C _sp3 –H amination

Journal Article · Sat Dec 31 23:00:00 EST 2016 · Faraday Discussions · OSTI ID:1393654

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

On the mechanism of intermolecular nitrogen-atom transfer from a lattice-isolated diruthenium nitride intermediate

Citation Formats

References (55)

Linked Research (1)

Similar Records

Related Subjects