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Characterization of Group 10‐Metal‐ p ‐Substituted Phenoxyl Radical Complexes with Schiff Base Ligands.
Author(s) -
Oshita Hiromi,
Kikuchi Misa,
Mieda Kaoru,
Ogura Takashi,
Yoshimura Takayoshi,
Tani Fumito,
Yajima Tatsuo,
Abe Hitoshi,
Mori Seiji,
Shimazaki Yuichi
Publication year - 2017
Publication title -
chemistryselect
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.437
H-Index - 34
ISSN - 2365-6549
DOI - 10.1002/slct.201701986
Subject(s) - chemistry , galactose oxidase , moiety , metal , ligand (biochemistry) , schiff base , aldehyde , polymer chemistry , metal ions in aqueous solution , photochemistry , stereochemistry , medicinal chemistry , organic chemistry , galactose , catalysis , biochemistry , receptor
Methylthiophenoxyl radical plays an important role as the active form of galactose oxidase (GO), which catalyzes oxidation of a primary alcohol to the corresponding aldehyde. Although many metal(II)‐phenoxyl radical species have been reported, only a few studies have been reported on the properties of methylthiophenoxyl radical‐metal complexes. We have prepared the group 10 metal (Ni, Pd and Pt) complexes of a salen‐type ligand with a methylthio group at para ‐position of the two phenolate moieties and characterized them by X‐ray crystal structure analyses and various spectroscopic methods in order to understand the role of the methylthio moiety in phenoxyl radical metal complexes. The corresponding p ‐methoxy substituted derivatives have been also characterized for comparison. All the one‐electron oxidized group 10 metal methylthiophenolate complexes have a relatively localized radical site on one of the two phenolate moieties in comparison to the one‐electron oxidized complexes of p ‐methoxy derivatives and exhibit different properties dependent on the central metal ions.