A Combined NRVS and DFT Study of FeIV[DOUBLE BOND]O Model Complexes: A Diagnostic Method for the Elucidation of Non-Heme Iron Enzyme Intermediates


  • NRVS=nuclear vibrational resonance spectroscopy. Use of the Advanced Photon Source at Argonne National Laboratory was supported by the U. S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357. Financial support of this research was provided by NIH Grants GM65440 (S.P.C), GM33162 (L.Q.), and GM40392 (E.I.S.) and NSF-Biophysics Program Grant MCB-0342807 (E.I.S). We would like to thank Jiyong Zhao, Wolfgang Sturhahn, and the staff at beamline 3-ID for assistance and discussions regarding NRVS.


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In the swing of things: FeIV[DOUBLE BOND]O biomimetic model complexes (see picture, Fe green, O red, N blue, C black) have been characterized using nuclear vibrational resonance spectroscopy. Systematic trends in the low-energy region reflect equatorial and axial bonding differences that relate to differences in reactivity. These trends have been computationally extended to predict the spectra of putative FeIV[DOUBLE BOND]O intermediates in non-heme iron enzymes.