Structural and spectroscopic characterization of an Fe(VI) bis(imido) complex

Jorge L. Martinez, Sean A. Lutz, Hao Yang, Jiaze Xie, Joshua Telser, Brian M. Hoffman, Veronica Carta, Maren Pink, Yaroslav Losovyj, Jeremy M. Smith*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

53 Scopus citations

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 languageEnglish (US)
Pages (from-to)356-359
Number of pages4
JournalScience
Volume370
Issue number6514
DOIs
StatePublished - 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

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