TITLE:
Recent Advances in X-Ray Structures of Metal-Phenoxyl Radical Complexes
AUTHORS:
Yuichi Shimazaki
KEYWORDS:
Phenoxyl Radical; Metal Complexes; Oxidation; Valence State; Crystal Structure; Electronic Structure; Reactivity
JOURNAL NAME:
Advances in Materials Physics and Chemistry,
Vol.3 No.1A,
April
26,
2013
ABSTRACT: An “experimental” valence state of metal complexes is
sometime different from the “formal” oxidation state, especially in the species
having redox active ligands. This difference can be seen in biological system,
such as iron(IV)-porphyrin π-cation radical in some heme proteins and
copper(II)-phenoxyl radical in galactose oxidase (GO). Although structural
characterizations of these species by X-ray diffraction methods have been rare
due to their stability, some artificial metal-phenoxyl radical complexes have
been synthesized and successfully characterized by X-ray crystal structure. In
this review, syntheses and X-ray crystal structures of the one-electron
oxidized metal-phenolate complexes, metal- phenoxyl radical,
and high-valent metal phenolate species are discussed.