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Experimental electronic structures of the FeIV=O bond in S=1 heme vs. nonheme sites: Effect of the porphyrin ligand

Journal Article · · Proceedings of the National Academy of Sciences
 [1];  [1];  [2];  [2];  [3];  [4];  [2];  [5];  [5];  [6];  [7];  [7];  [7];  [7];  [7];  [8];  [9];  [10];  [7];  [7] more »;  [5];  [6];  [1] « less
  1. Stanford Univ., CA (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
  2. Stanford Univ., CA (United States)
  3. Stanford Univ., CA (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL); Univ. of Manchester (United Kingdom); Harwell Science and Innovation Campus, Didcot (United Kingdom). Diamond Light Source, Ltd.
  4. Stanford Univ., CA (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL); Argonne National Laboratory (ANL), Argonne, IL (United States)
  5. Johns Hopkins Univ., Baltimore, MD (United States)
  6. Univ. of Minnesota, Minneapolis, MN (United States)
  7. SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL); Stanford Univ., CA (United States)
  8. Japan Synchrotron Radiation Research Institute, Sayo, Hyogo (Japan)
  9. Kyoto Univ. (Japan)
  10. RIKEN SPring-8 Center, Sayo (Japan)
+ Show Author Affiliations
High-valent FeIV=O species are common intermediates in biological and artificial catalysts. Heme and nonheme S=1 FeIV=O sites have been synthesized and studied for decades but little quantitative experimental comparison of their electronic structures has been available, due to the lack of direct methods focused on the iron. This study allows a rigorous determination of the electronic structure of a nonheme FeIV=O center and its comparison to an FeIV=O heme site using 1s2p resonant inelastic X-ray scattering (RIXS) and Fe L-edge X-ray absorption spectroscopy (XAS). Further, variable temperature magnetic circular dichroism (VT-MCD) of the ligand field transitions, combined with nuclear resonance vibrational spectroscopy of the two S=1 FeIV=O systems show that the equatorial ligand field decreases from a nonheme to a heme FeIV=O site. Alternatively, RIXS and Fe L-edge XAS combined with MCD show that the Fe dπ orbitals are unperturbed in the FeIV=O heme relative to the nonheme site because the strong axial Fe-O bond uncouples the Fe dπ orbitals from the porphyrin π-system. As a consequence, the thermodynamics and kinetics of the H-atom abstraction reactions are actually very similar for heme compound II and nonheme FeIV=O active sites.
Research Organization:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Sponsoring Organization:
National Institutes of Health (NIH); USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Biological and Environmental Research (BER)
Grant/Contract Number:
AC02-76SF00515
OSTI ID:
2587857
Journal Information:
Proceedings of the National Academy of Sciences, Journal Name: Proceedings of the National Academy of Sciences Journal Issue: 8 Vol. 122; ISSN 1091-6490; ISSN 0027-8424
Publisher:
Proceedings of the National Academy of SciencesCopyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

bioinorganic chemistry
mononuclear iron centers
spectroscopy