Experimental and theoretical identification of the Fe(VII) oxidation state in FeO4−

Jun-Bo Lu; Jiwen Jian; Wei Huang; Hailu Lin; Jun Li; Mingfei Zhou

doi:10.1039/C6CP06753K

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Experimental and theoretical identification of the Fe(vii) oxidation state in FeO₄⁻†

Jun-Bo Lu,‡^a Jiwen Jian,‡^b Wei Huang,^a Hailu Lin,^b Jun Li

*^a and Mingfei Zhou*^b

Author affiliations

* Corresponding authors

^a Department of Chemistry and Key Laboratory of Organic Optoelectronics & Molecular Engineering of Ministry of Education, Tsinghua University, Beijing 100084, China
E-mail: junli@tsinghua.edu.cn

^b Collaborative Innovation Center of Chemistry for Energy Materials, Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysts and Innovative Materials, Fudan University, Shanghai 200433, China
E-mail: mfzhou@fudan.edu.cn

Abstract

The experimentally known highest oxidation state of iron has been determined to be Fe(VI) so far. Here we report a combined matrix-isolation infrared spectroscopic and theoretical study of two interconvertible iron oxide anions: a dioxoiron peroxide complex [(η²-O₂)FeO₂]⁻ with a C_2v-structure and a tetroxide FeO₄⁻ with a D_2d tetrahedral structure, which are formed by co-condensation of laser-ablated iron atoms and electrons with O₂/Ar mixtures at 4 K. Quantum chemistry theoretical studies indicate that the Jahn–Teller distorted tetroxide FeO₄⁻ anion is a d¹ species with hereto the highest iron formal oxidation state Fe(VII).

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Article information

DOI: https://doi.org/10.1039/C6CP06753K
Article type: Paper
Submitted: 02 Oct 2016
Accepted: 19 Oct 2016
First published: 19 Oct 2016

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Phys. Chem. Chem. Phys., 2016,18, 31125-31131

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Experimental and theoretical identification of the Fe(VII) oxidation state in FeO₄⁻

J. Lu, J. Jian, W. Huang, H. Lin, J. Li and M. Zhou, Phys. Chem. Chem. Phys., 2016, 18, 31125 DOI: 10.1039/C6CP06753K

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