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Abstract
Enzymatic haem and non-haem high-valent iron-oxo species are known to activate strong C-H bonds, yet duplicating this reactivity in a synthetic system remains a formidable challenge. Although instability of the terminal iron-oxo moiety is perhaps the foremost obstacle, steric and electronic factors also limit the activity of previously reported mononuclear iron(IV)-oxo compounds. In particular, although nature's non-haem iron(IV)-oxo compounds possess high-spin S = 2 ground states, this electronic configuration has proved difficult to achieve in a molecular species. These challenges may be mitigated within metal-organic frameworks that feature site-isolated iron centres in a constrained, weak-field ligand environment. Here, we show that the metal-organic framework Fe2 (dobdc) (dobdc4- = 2,5-dioxido-1,4- benzenedicarboxylate) and its magnesium-diluted analogue, Fe0.1 Mg1.9 (dobdc), are able to activate the C-H bonds of ethane and convert it into ethanol and acetaldehyde using nitrous oxide as the terminal oxidant. Electronic structure calculations indicate that the active oxidant is likely to be a high-spin S = 2 iron(IV)-oxo species.
Original language | English (US) |
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Pages (from-to) | 590-595 |
Number of pages | 6 |
Journal | Nature Chemistry |
Volume | 6 |
Issue number | 7 |
DOIs | |
State | Published - Jul 2014 |
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Dive into the research topics of 'Oxidation of ethane to ethanol by N2 O in a metal-organic framework with coordinatively unsaturated iron(II) sites'. Together they form a unique fingerprint.Projects
- 1 Finished
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NMGC: Nanoporous Materials Genome: Methods and Software to Optimize Gas Storage, Separations, and Catalysis (Phase 1)
Siepmann, I., Cramer, C., Gagliardi, L., Truhlar, D. G., Tsapatsis, M. & Goodpaster, J. D.
9/1/12 → 8/31/17
Project: Research project