Abstract
High-valent iron species are key intermediates in oxidative biological processes, but hexavalent complexes apart from the ferrate ion are exceedingly rare. Here, we report the synthesis and structural and spectroscopic characterization of a stable Fe(VI) complex (3) prepared by facile one-electron oxidation of an Fe(V) bis(imido) (2). Single-crystal x-ray diffraction of 2 and 3 revealed four-coordinate Fe centers with an unusual “seesaw” geometry. 57Fe Mössbauer, x-ray photoelectron, x-ray absorption, and electron-nuclear double resonance (ENDOR) spectroscopies, supported by electronic structure calculations, support a low-spin (S = 1/2) d3 Fe(V) configuration in 2 and a diamagnetic (S = 0) d2 Fe(VI) configuration in 3. Their shared seesaw geometry is electronically dictated by a balance of Fe-imido s- and p-bonding interactions.
| Original language | English (US) |
|---|---|
| Pages (from-to) | 356-359 |
| Number of pages | 4 |
| Journal | Science |
| Volume | 370 |
| Issue number | 6514 |
| DOIs | |
| State | Published - Oct 16 2020 |
Funding
Funding from the NSF is gratefully acknowledged by J.L.M., S.A.L., and J.M.S. (CHE-1566258) and B.M.H. (MCB-1515981). This material is based upon work supported by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences under award nos. DE-SC0019466 (to J.M.S.) and DE-SC0019342 (to B.M.H.). The XPS instrument at the IU Nanoscale Characterization Facility was funded by the NSF (DMR MRI-1126394). Support for the acquisition of the Bruker Venture D8 diffractometer through the Major Scientific Research Equipment Fund from the President of Indiana University and the Office of the Vice President for Research is gratefully acknowledged. NSF's ChemMatCARS Sector 15 is supported by the NSF Divisions of Chemistry (CHE) and Materials Research (DMR) under grant no. CHE-1834750. Use of the Advanced Photon Source, an Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory, was supported by DOE under contract no. DE-AC02-06CH11357.
ASJC Scopus subject areas
- General
Fingerprint
Dive into the research topics of 'Structural and spectroscopic characterization of an Fe(VI) bis(imido) complex'. Together they form a unique fingerprint.Datasets
-
CCDC 1990355: Experimental Crystal Structure Determination
Martinez, J. L. (Contributor), Lutz, S. A. (Contributor), Yang, H. (Contributor), Xie, J. (Contributor), Telser, J. (Contributor), Hoffman, B. M. (Contributor), Carta, V. (Contributor), Pink, M. (Contributor), Losovyj, Y. (Contributor) & Smith, J. M. (Contributor), Cambridge Crystallographic Data Centre, 2020
DOI: 10.5517/ccdc.csd.cc24t404, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc24t404&sid=DataCite
Dataset
-
CCDC 1990354: Experimental Crystal Structure Determination
Martinez, J. L. (Contributor), Lutz, S. A. (Contributor), Yang, H. (Contributor), Xie, J. (Contributor), Telser, J. (Contributor), Hoffman, B. M. (Contributor), Carta, V. (Contributor), Pink, M. (Contributor), Losovyj, Y. (Contributor) & Smith, J. M. (Contributor), Cambridge Crystallographic Data Centre, 2020
DOI: 10.5517/ccdc.csd.cc24t3z2, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc24t3z2&sid=DataCite
Dataset
-
CCDC 1990356: Experimental Crystal Structure Determination
Martinez, J. L. (Contributor), Lutz, S. A. (Contributor), Yang, H. (Contributor), Xie, J. (Contributor), Telser, J. (Contributor), Hoffman, B. M. (Contributor), Carta, V. (Contributor), Pink, M. (Contributor), Losovyj, Y. (Contributor) & Smith, J. M. (Contributor), Cambridge Crystallographic Data Centre, 2020
DOI: 10.5517/ccdc.csd.cc24t415, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc24t415&sid=DataCite
Dataset