title: Oxidation of ethane to ethanol by N2O in a metal-organic framework with coordinatively unsaturated iron(II) sites.
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) (dobdc(4-) = 2,5-dioxido-1,4-benzenedicarboxylate) and its magnesium-diluted analogue, Fe0.1Mg1.9(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.
authors.affiliation: Department of Chemistry, University of California, Berkeley, California 94720-1460, USA.
authors.forename: Dianne J
authors.initials: DJ
authors.lastname: Xiao
authors.affiliation: Department of Chemistry, University of California, Berkeley, California 94720-1460, USA.
authors.forename: Eric D
authors.initials: ED
authors.lastname: Bloch
authors.affiliation: Department of Chemistry, University of California, Berkeley, California 94720-1460, USA.
authors.forename: Jarad A
authors.initials: JA
authors.lastname: Mason
authors.affiliation: The Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, California 94720-1460, USA.
authors.forename: Wendy L
authors.initials: WL
authors.lastname: Queen
authors.affiliation: Center for Neutron Research, National Institute of Standards and Technology, Gaithersburg, Maryland 20899, USA.
authors.forename: Matthew R
authors.initials: MR
authors.lastname: Hudson
authors.affiliation: Department of Chemistry, Chemical Theory Center, and Supercomputing Institute, University of Minnesota, Minneapolis, Minnesota, 55455-0431, USA.
authors.forename: Nora
authors.initials: N
authors.lastname: Planas
authors.affiliation: Department of Chemistry, Chemical Theory Center, and Supercomputing Institute, University of Minnesota, Minneapolis, Minnesota, 55455-0431, USA.
authors.forename: Joshua
authors.initials: J
authors.lastname: Borycz
authors.affiliation: Department of Chemistry, Chemical Theory Center, and Supercomputing Institute, University of Minnesota, Minneapolis, Minnesota, 55455-0431, USA.
authors.forename: Allison L
authors.initials: AL
authors.lastname: Dzubak
authors.affiliation: Department of Chemistry, Chemical Theory Center, and Supercomputing Institute, University of Minnesota, Minneapolis, Minnesota, 55455-0431, USA.
authors.forename: Pragya
authors.initials: P
authors.lastname: Verma
authors.affiliation: The Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, California 94720-1460, USA.
authors.forename: Kyuho
authors.identifier: 0000000193253717
authors.initials: K
authors.lastname: Lee
authors.affiliation: Department of Chemistry, NIS and INSTM Reference Centres, University of Turin, I-10135 Torino, Italy.
authors.forename: Francesca
authors.initials: F
authors.lastname: Bonino
authors.affiliation: Department of Chemistry, NIS and INSTM Reference Centres, University of Turin, I-10135 Torino, Italy.
authors.forename: Valentina
authors.initials: V
authors.lastname: Crocellà
authors.affiliation: Physical Biosciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720-1460, USA.
authors.forename: Junko
authors.initials: J
authors.lastname: Yano
authors.affiliation: Department of Chemistry, NIS and INSTM Reference Centres, University of Turin, I-10135 Torino, Italy.
authors.forename: Silvia
authors.initials: S
authors.lastname: Bordiga
authors.affiliation: Department of Chemistry, Chemical Theory Center, and Supercomputing Institute, University of Minnesota, Minneapolis, Minnesota, 55455-0431, USA.
authors.forename: Donald G
authors.initials: DG
authors.lastname: Truhlar
authors.affiliation: Department of Chemistry, Chemical Theory Center, and Supercomputing Institute, University of Minnesota, Minneapolis, Minnesota, 55455-0431, USA.
authors.forename: Laura
authors.initials: L
authors.lastname: Gagliardi
authors.affiliation: 1] Center for Neutron Research, National Institute of Standards and Technology, Gaithersburg, Maryland 20899, USA [2] Department of Chemical Engineering, University of Delaware, Newark, Delaware 19716, USA.
authors.forename: Craig M
authors.initials: CM
authors.lastname: Brown
authors.affiliation: 1] Department of Chemistry, University of California, Berkeley, California 94720-1460, USA [2] Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA.
authors.forename: Jeffrey R
authors.initials: JR
authors.lastname: Long
mesh_terms: D004980:Ethane / Q000737:chemistry*; D000431:Ethanol / Q000737:chemistry*; D007501:Iron / Q000737:chemistry*; D008958:Models, Molecular; D010084:Oxidation-Reduction
chemical_list: D000431:Ethanol; D007501:Iron; D004980:Ethane