Structural characterization of a non-heme iron active site in zeolites that hydroxylates methane

Snyder, Benjamin E. R.; Böttger, Lars H.; Bols, Max L.; Yan, James J.; Rhoda, Hannah M.; Jacobs, Ariel B.; Hu, Michael Y.; Zhao, Jiyong; Alp, E. Ercan; Hedman, Britt; Hodgson, Keith O.; Schoonheydt, Robert A.; Sels, Bert F.; Solomon, Edward I.

doi:10.1073/pnas.1721717115

Title: Structural characterization of a non-heme iron active site in zeolites that hydroxylates methane

Journal Article · Mon Apr 02 00:00:00 EDT 2018 · Proceedings of the National Academy of Sciences of the United States of America

DOI:https://doi.org/10.1073/pnas.1721717115· OSTI ID:1430783

Snyder, Benjamin E. R. ^[1]; Böttger, Lars H. ^[1]; Bols, Max L. ^[2]; Yan, James J. ^[1]; Rhoda, Hannah M. ^[1]; Jacobs, Ariel B. ^[1];

^[3]; Zhao, Jiyong ^[3]; Alp, E. Ercan ^[3]; Hedman, Britt ^[4]; Hodgson, Keith O. ^[5]; Schoonheydt, Robert A. ^[2]; Sels, Bert F. ^[2]; Solomon, Edward I. ^[5]

Department of Chemistry, Stanford University, Stanford, CA 94305,
Department of Microbial and Molecular Systems, Centre for Surface Chemistry and Catalysis, KU Leuven, B-3001 Leuven, Belgium,
Advanced Photon Source, Argonne National Laboratory, Argonne, IL 60439,
Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, Menlo Park, CA 94025
Department of Chemistry, Stanford University, Stanford, CA 94305,, Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, Menlo Park, CA 94025

Iron-containing zeolites exhibit unprecedented reactivity in the low-temperature hydroxylation of methane to form methanol. Reactivity occurs at a mononuclear ferrous active site, α-Fe(II), that is activated by N₂O to form the reactive intermediate α-O. This has been defined as an Fe(IV)=O species. Using nuclear resonance vibrational spectroscopy coupled to X-ray absorption spectroscopy, we probe the bonding interaction between the iron center, its zeolite lattice-derived ligands, and the reactive oxygen. α-O is found to contain an unusually strong Fe(IV)=O bond resulting from a constrained coordination geometry enforced by the zeolite lattice. As a result, density functional theory calculations clarify how the experimentally determined geometric structure of the active site leads to an electronic structure that is highly activated to perform H-atom abstraction.

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Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE; National Science Foundation (NSF)

Grant/Contract Number:: AC02-06CH11357; CHE-1660611; G0A2216N; P41GM103393; DGE-11474; AC02-76SF00515

OSTI ID:: 1430783

Alternate ID(s):: OSTI ID: 1457409; OSTI ID: 1466306

Journal Information:: Proceedings of the National Academy of Sciences of the United States of America, Journal Name: Proceedings of the National Academy of Sciences of the United States of America Vol. 115 Journal Issue: 18; ISSN 0027-8424

Publisher:: Proceedings of the National Academy of SciencesCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 56 works

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46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND TECHNOLOGY
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nuclear resonance vibrational spectroscopy
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Title: Structural characterization of a non-heme iron active site in zeolites that hydroxylates methane

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