Alpha-oxygen

Alpha-oxygen (α-O) is a reactive oxygen species formed from an oxygen-atom abstraction (OAT) from nitrous oxide (N2O) by alpha-iron (α-Fe) catalysts. The latter is defined as a high spin (S=2) divalent iron(II) ion in a constrained square planar coordination with an accessible axial coordination position. The stabilization of α-O requires structural strain on the equatorial ligand field to maintain the reactive oxygen atom in the axial position and it is this forced geometry, similar to the 'entatic state' known in metalloproteins, that lies at the basis of its reactivity in inert C-H bond activation.[1]

Alpha-oxygen
Names
Other names
Alpha-O, α-O
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Infobox references

The alpha-oxygen site was first discovered and named in 1990 by researchers from the Boreskov Institute of Catalysis in the ZSM-5 zeolite,[2][3] and was later described in detail by researchers from Stanford University and KU Leuven in the beta zeolite.[1][4][5]

See also

References
  1. Snyder BE, Vanelderen P, Bols ML, Hallaert SD, Böttger LH, Ungur L, Pierloot K, Schoonheydt RA, Sels BF, Solomon EI (August 2016). "The active site of low-temperature methane hydroxylation in iron-containing zeolites". Nature. 536 (7616): 317–21. doi:10.1038/nature19059. PMID 27535535.
  2. Pannov GI, Sobolev VI, Kharitonov AS (July 1990). "The role of iron in N2O decomposition on ZSM-5 zeolite and reactivity of the surface oxygen formed". Journal of Molecular Catalysis. 61 (1): 85–97. doi:10.1016/0304-5102(90)85197-P.
  3. Sobolev V (February 1993). "Catalytic Properties of ZSM-5 Zeolites in N2O Decomposition: The Role of Iron". Journal of Catalysis. 139 (2): 435–443. doi:10.1006/jcat.1993.1038.
  4. Hallaert SD, Bols ML, Vanelderen P, Schoonheydt RA, Sels BF, Pierloot K (September 2017). "Identification of α-Fe in High-Silica Zeolites on the Basis of ab Initio Electronic Structure Calculations". Inorganic Chemistry. 56 (17): 10681–10690. doi:10.1021/acs.inorgchem.7b01653. PMID 28836775.
  5. Snyder BE, Böttger LH, Bols ML, Yan JJ, Rhoda HM, Jacobs AB, Hu MY, Zhao J, Alp EE, Hedman B, Hodgson KO, Schoonheydt RA, Sels BF, Solomon EI (May 2018). "Structural characterization of a non-heme iron active site in zeolites that hydroxylates methane". Proceedings of the National Academy of Sciences of the United States of America. 115 (18): 4565–4570. doi:10.1073/pnas.1721717115. PMC 5939097. PMID 29610304.
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