Selective Catalytic Olefin Epoxidation with Mn[superscript II]-Exchanged MOF-5
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Author(s)
Braglia, Luca
Borfecchia, Elisa
Meyer, Randall J.
Román- Leshkov, Yuriy
Lamberti, Carlo
Stubbs, Amanda Walcott
Dinca, Mircea
Date Issued
January 2018
Journal
ACS Catalysis
Citation
Stubbs, Amanda W. et al. “Selective Catalytic Olefin Epoxidation with Mn[superscript II]-Exchanged MOF-5.” ACS Catalysis 8, 1 (December 2017): 596–601 © 2017 American Chemical Society
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Author's final manuscript
Abstract
Partial substitution of Zn[superscript II] by Mn[superscript II] in Zn₄O(terephthalate)₃(MOF-5) leads to a distorted all-oxygen ligand field supporting a single MnII site, whose structure was confirmed by Mn K-edge X-ray absorption spectroscopy. The Mn[superscript II] ion at the MOF-5 node engages in redox chemistry with a variety of oxidants. With [superscript t]BuSO₂PhIO, it produces a putative Mn[superscript IV]-oxo intermediate, which upon further reaction with adventitious hydrogen is trapped as a Mn[superscript III]–OH species. Most intriguingly, the intermediacy of the high-spin Mn[superscript IV]–oxo species is likely responsible for catalytic activity of the Mn[superscript II]-MOF-5 precatalyst, which in the presence of [superscript t]BuSO₂PhIO catalyzes oxygen atom transfer reactivity to form epoxides from cyclic alkenes with >99% selectivity. These results demonstrate that MOF secondary building units serve as competent platforms for accessing terminal high-valent metal–oxo species that consequently engage in catalytic oxygen atom transfer chemistry owing to the relatively weak ligand fields provided by the SBU. Keywords: alkene epoxidation; heterogeneous catalysis; manganese(III)−hydroxo; manganese(IV)−oxo; metal−organic framework; oxidation; tert-butylsulfonyl-2-iodosylbenzene
MIT Department
Massachusetts Institute of Technology. Department of Chemical Engineering
Massachusetts Institute of Technology. Department of Chemistry
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DOI of Published Version
https://doi.org/10.1021/acscatal.7b02946
