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Nuclear Resonance Vibrational Spectroscopic Definition of Peroxy Intermediates in Nonheme Iron Sites

Title
Nuclear Resonance Vibrational Spectroscopic Definition of Peroxy Intermediates in Nonheme Iron Sites
Authors
Sutherlin K.D.Liu L.V.Lee Y.-M.Kwak Y.Yoda Y.Saito M.Kurokuzu M.Kobayashi Y.Seto M.Que L.Nam W.Solomon E.I.
Ewha Authors
남원우이용민
SCOPUS Author ID
남원우scopus; 이용민scopusscopus
Issue Date
2016
Journal Title
Journal of the American Chemical Society
ISSN
0002-7863JCR Link
Citation
vol. 138, no. 43, pp. 14294 - 14302
Publisher
American Chemical Society
Indexed
SCI; SCIE; SCOPUS WOS scopus
Abstract
FeIII-(hydro)peroxy intermediates have been isolated in two classes of mononuclear nonheme Fe enzymes that are important in bioremediation: the Rieske dioxygenases and the extradiol dioxygenases. The binding mode and protonation state of the peroxide moieties in these intermediates are not well-defined, due to a lack of vibrational structural data. Nuclear resonance vibrational spectroscopy (NRVS) is an important technique for obtaining vibrational information on these and other intermediates, as it is sensitive to all normal modes with Fe displacement. Here, we present the NRVS spectra of side-on FeIII-peroxy and end-on FeIII-hydroperoxy model complexes and assign these spectra using calibrated DFT calculations. We then use DFT calculations to define and understand the changes in the NRVS spectra that arise from protonation and from opening the Fe-O-O angle. This study identifies four spectroscopic handles that will enable definition of the binding mode and protonation state of FeIII-peroxy intermediates in mononuclear nonheme Fe enzymes. These structural differences are important in determining the frontier molecular orbitals available for reactivity. © 2016 American Chemical Society.
DOI
10.1021/jacs.6b07227
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자연과학대학 > 화학·나노과학전공 > Journal papers
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