High–Valent Metal–Oxo Species at the Nodes of Metal–Triazolate Frameworks: The Effects of Ligand Exchange and Two–State Reactivity for C–H Bond Activation

Rosen, Andrew S.; Notestein, Justin M.; Snurr, Randall Q.

doi:10.1002/anie.202004458

High–Valent Metal–Oxo Species at the Nodes of Metal–Triazolate Frameworks: The Effects of Ligand Exchange and Two–State Reactivity for C–H Bond Activation

Journal Article · Sun Mar 29 00:00:00 EDT 2020 · Angewandte Chemie (International Edition)

DOI:https://doi.org/10.1002/anie.202004458· OSTI ID:2482448

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Northwestern University, Evanston, IL (United States)

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. Here, 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.

View Accepted Manuscript (DOE)

Research Organization:: Northwestern University, Evanston, IL (United States)

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

Grant/Contract Number:: FG02-03ER15457

OSTI ID:: 2482448

Alternate ID(s):: OSTI ID: 1617537
OSTI ID: 1849441

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 44 Vol. 59; ISSN 1433-7851

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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