TY - JOUR
T1 - High-Valent Metal–Oxo Species at the Nodes of Metal–Triazolate Frameworks
T2 - The Effects of Ligand Exchange and Two-State Reactivity for C−H Bond Activation
AU - Rosen, Andrew S.
AU - Notestein, Justin M.
AU - Snurr, Randall Q.
N1 - Funding Information:
A.S.R. was supported by a fellowship award through the National Defense Science and Engineering Graduate (NDSEG) Fellowship Program and a Ryan Fellowship through the International Institute for Nanotechnology at Northwestern University. The authors acknowledge computing support through the Quest high‐performance computing facility at Northwestern University, the DOD High Performance Computing Modernization Program at the Air Force Research Laboratory, and the Extreme Science and Engineering Discovery Environment (XSEDE) Stampede2 through allocation CTS180057 supported by National Science Foundation grant number ACI‐1548562. The material in this work is supported by the Institute for Catalysis in Energy Processes (ICEP) via the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award Number DE‐FG02‐03ER15457. R.Q.S. thanks the 111 Project (Grant No. B17020) for support to visit Jilin University and Prof. Jihong Yu and Prof. Yi Li for stimulating discussions.
Funding Information:
A.S.R. was supported by a fellowship award through the National Defense Science and Engineering Graduate (NDSEG) Fellowship Program and a Ryan Fellowship through the International Institute for Nanotechnology at Northwestern University. The authors acknowledge computing support through the Quest high-performance computing facility at Northwestern University, the DOD High Performance Computing Modernization Program at the Air Force Research Laboratory, and the Extreme Science and Engineering Discovery Environment (XSEDE) Stampede2 through allocation CTS180057 supported by National Science Foundation grant number ACI-1548562. The material in this work is supported by the Institute for Catalysis in Energy Processes (ICEP) via the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award Number DE-FG02-03ER15457. R.Q.S. thanks the 111 Project (Grant No. B17020) for support to visit Jilin University and Prof. Jihong Yu and Prof. Yi Li for stimulating discussions.
Publisher Copyright:
© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
PY - 2020/10/26
Y1 - 2020/10/26
N2 - Through quantum-chemical calculations, we investigate a family of metal–organic frameworks (MOFs) containing triazolate linkers, M2X2(BBTA) (M=metal, X=bridging anion, H2BBTA=1H,5H-benzo(1,2-d:4,5-d′)bistriazole), for their ability to form terminal metal–oxo sites and subsequently activate the C−H bond of methane. By varying the metal and bridging anion in the framework, we show how to significantly tune the reactivity of this series of MOFs. The electronic structure of the metal–oxo active site is analyzed for each combination of metal and bridging ligand, and we find that spin density localized on the oxo ligand is not an inherent requirement for low C−H activation barriers. For the Mn- and Fe-containing frameworks, a transition from ferromagnetic to antiferromagnetic coupling between the metal binding site and terminal oxo ligand during the C−H activation process can greatly reduce the kinetic barrier, a unique case of two-state reactivity without a change in the net spin multiplicity.
AB - Through quantum-chemical calculations, we investigate a family of metal–organic frameworks (MOFs) containing triazolate linkers, M2X2(BBTA) (M=metal, X=bridging anion, H2BBTA=1H,5H-benzo(1,2-d:4,5-d′)bistriazole), for their ability to form terminal metal–oxo sites and subsequently activate the C−H bond of methane. By varying the metal and bridging anion in the framework, we show how to significantly tune the reactivity of this series of MOFs. The electronic structure of the metal–oxo active site is analyzed for each combination of metal and bridging ligand, and we find that spin density localized on the oxo ligand is not an inherent requirement for low C−H activation barriers. For the Mn- and Fe-containing frameworks, a transition from ferromagnetic to antiferromagnetic coupling between the metal binding site and terminal oxo ligand during the C−H activation process can greatly reduce the kinetic barrier, a unique case of two-state reactivity without a change in the net spin multiplicity.
KW - C−H activation
KW - density functional theory
KW - ligand exchange
KW - metal–organic framework
KW - spin
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U2 - 10.1002/anie.202004458
DO - 10.1002/anie.202004458
M3 - Article
C2 - 32227416
AN - SCOPUS:85085063697
VL - 59
SP - 19494
EP - 19502
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
SN - 1433-7851
IS - 44
ER -