Oxidation of ethane to ethanol by N2 O in a metal-organic framework with coordinatively unsaturated iron(II) sites

Dianne J. Xiao, Eric D. Bloch, Jarad A. Mason, Wendy L. Queen, Matthew R. Hudson, Nora Planas, Joshua Borycz, Allison L. Dzubak, Pragya Verma, Kyuho Lee, Francesca Bonino, Valentina Crocellà, Junko Yano, Silvia Bordiga, Donald G. Truhlar, Laura Gagliardi, Craig M. Brown, Jeffrey R. Long

Research output: Contribution to journalArticle

226 Scopus citations

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 languageEnglish (US)
Pages (from-to)590-595
Number of pages6
JournalNature Chemistry
Volume6
Issue number7
DOIs
StatePublished - Jul 2014

Fingerprint Dive into the research topics of 'Oxidation of ethane to ethanol by N<sub>2</sub> O in a metal-organic framework with coordinatively unsaturated iron(II) sites'. Together they form a unique fingerprint.

  • Projects

    Cite this

    Xiao, D. J., Bloch, E. D., Mason, J. A., Queen, W. L., Hudson, M. R., Planas, N., Borycz, J., Dzubak, A. L., Verma, P., Lee, K., Bonino, F., Crocellà, V., Yano, J., Bordiga, S., Truhlar, D. G., Gagliardi, L., Brown, C. M., & Long, J. R. (2014). Oxidation of ethane to ethanol by N2 O in a metal-organic framework with coordinatively unsaturated iron(II) sites. Nature Chemistry, 6(7), 590-595. https://doi.org/10.1038/nchem.1956