Experimental and theoretical identification of the Fe(vii) oxidation state in FeO4.
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 C2v-structure and a tetroxide FeO4-with a D2dtetrahedral 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 d1species with hereto the highest iron formal oxidation state Fe(vii).
Department of Chemistry and Key Laboratory of Organic Optoelectronics & Molecular Engineering of Ministry of Education, Tsinghua University, Beijing 100084, China. junli@tsinghua.edu.cn.
Jun-Bo
JB
Lu
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. mfzhou@fudan.edu.cn.
Jiwen
J
Jian
Department of Chemistry and Key Laboratory of Organic Optoelectronics & Molecular Engineering of Ministry of Education, Tsinghua University, Beijing 100084, China. junli@tsinghua.edu.cn.
Wei
W
Huang
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. mfzhou@fudan.edu.cn.
Hailu
H
Lin
Department of Chemistry and Key Laboratory of Organic Optoelectronics & Molecular Engineering of Ministry of Education, Tsinghua University, Beijing 100084, China. junli@tsinghua.edu.cn.
Jun
http://orcid.org/0000-0002-8456-3980
J
Li
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. mfzhou@fudan.edu.cn.
Mingfei
M
Zhou