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

Kyle D. Sutherlin, Lei V. Liu, Yong Min Lee, Yeonju Kwak, Yoshitaka Yoda, Makina Saito, Masayuki Kurokuzu, Yasuhiro Kobayashi, Makoto Seto, Lawrence Que, Wonwoo Nam, Edward I. Solomon

Research output: Contribution to journalArticle

3 Citations (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.

Original languageEnglish (US)
Pages (from-to)14294-14302
Number of pages9
JournalJournal of the American Chemical Society
Volume138
Issue number43
DOIs
StatePublished - Nov 2 2016

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Vibrational spectroscopy
Protonation
Spectrum Analysis
Iron
Discrete Fourier transforms
Enzymes
Dioxygenases
Environmental Biodegradation
Bioremediation
Peroxides
Molecular orbitals

Cite this

Sutherlin, K. D., Liu, L. V., Lee, Y. M., Kwak, Y., Yoda, Y., Saito, M., ... Solomon, E. I. (2016). Nuclear Resonance Vibrational Spectroscopic Definition of Peroxy Intermediates in Nonheme Iron Sites. Journal of the American Chemical Society, 138(43), 14294-14302. https://doi.org/10.1021/jacs.6b07227

Nuclear Resonance Vibrational Spectroscopic Definition of Peroxy Intermediates in Nonheme Iron Sites. / Sutherlin, Kyle D.; Liu, Lei V.; Lee, Yong Min; Kwak, Yeonju; Yoda, Yoshitaka; Saito, Makina; Kurokuzu, Masayuki; Kobayashi, Yasuhiro; Seto, Makoto; Que, Lawrence; Nam, Wonwoo; Solomon, Edward I.

In: Journal of the American Chemical Society, Vol. 138, No. 43, 02.11.2016, p. 14294-14302.

Research output: Contribution to journalArticle

Sutherlin, KD, Liu, LV, Lee, YM, Kwak, Y, Yoda, Y, Saito, M, Kurokuzu, M, Kobayashi, Y, Seto, M, Que, L, Nam, W & Solomon, EI 2016, 'Nuclear Resonance Vibrational Spectroscopic Definition of Peroxy Intermediates in Nonheme Iron Sites', Journal of the American Chemical Society, vol. 138, no. 43, pp. 14294-14302. https://doi.org/10.1021/jacs.6b07227
Sutherlin, Kyle D. ; Liu, Lei V. ; Lee, Yong Min ; Kwak, Yeonju ; Yoda, Yoshitaka ; Saito, Makina ; Kurokuzu, Masayuki ; Kobayashi, Yasuhiro ; Seto, Makoto ; Que, Lawrence ; Nam, Wonwoo ; Solomon, Edward I. / Nuclear Resonance Vibrational Spectroscopic Definition of Peroxy Intermediates in Nonheme Iron Sites. In: Journal of the American Chemical Society. 2016 ; Vol. 138, No. 43. pp. 14294-14302.
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