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X‐Ray Emission Spectroscopy: A Spectroscopic Measure for the Determination of NO Oxidation States in Fe–NO Complexes
Author(s) -
Lu TsaiTe,
Weng TsuChien,
Liaw WenFeng
Publication year - 2014
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201407603
Subject(s) - valence (chemistry) , oxidation state , spectroscopy , atomic orbital , chemistry , oxide , redox , crystallography , computational chemistry , analytical chemistry (journal) , inorganic chemistry , physics , metal , organic chemistry , quantum mechanics , electron , chromatography
Abstract Extensive study of the electronic structure of Fe‐NO complexes using a variety of spectroscopic methods was attempted to understand how iron controls the binding and release of nitric oxide. The comparable energy levels of NO π* orbitals and Fe 3d orbitals complicate the bonding interaction within FeNO complexes and puzzle the quantitative assignment of NO oxidation state. Enemark–Feltham notation, {Fe(NO) x } n , was devised to circumvent this puzzle. This 40‐year puzzle is revisited using valence‐to‐core X‐ray emission spectroscopy (V2C XES) in combination with computational study. DFT calculation establishes a linear relationship between ΔE σ2s*‐σ2p of NO and its oxidation state. V2C Fe XES study of FeNO complexes reveals the ΔE σ2s*‐σ2p of NO derived from NO σ 2s */σ 2p →Fe 1s transitions and determines NO oxidation state in FeNO complexes. Quantitative assignment of NO oxidation state will correlate the feasible redox process of nitric oxide and Fe‐nitrosylation biology.