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Three Distinct Redox States of an Oxo‐Bridged Dinuclear Ruthenium Complex
Author(s) -
Yoshida Masaki,
Kondo Mio,
Nakamura Toshikazu,
Sakai Ken,
Masaoka Shigeyuki
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.201406443
Subject(s) - ruthenium , redox , delocalized electron , crystallography , valence (chemistry) , chemistry , terpyridine , oxidation state , unpaired electron , crystal structure , electronic structure , stereochemistry , molecule , metal , inorganic chemistry , computational chemistry , catalysis , biochemistry , organic chemistry
A series of [{(terpy)(bpy)Ru}(μ‐O){Ru(bpy)(terpy)}] n+ ( [RuORu] n+ , terpy=2,2′;6′,2′′‐terpyridine, bpy=2,2′‐bipyridine) was systematically synthesized and characterized in three distinct redox states (n=3, 4, and 5 for Ru II,III 2 , Ru III,III 2 , and Ru III,IV 2 , respectively). The crystal structures of [RuORu] n+ (n=3, 4, 5) in all three redox states were successfully determined. X‐ray crystallography showed that the RuO distances and the Ru‐O‐Ru angles are mainly regulated by the oxidation states of the ruthenium centers. X‐ray crystallography and ESR spectra clearly revealed the detailed electronic structures of two mixed‐valence complexes, [Ru III ORu IV ] 5+ and [Ru II ORu III ] 3+ , in which each unpaired electron is completely delocalized across the oxo‐bridged dinuclear core. These findings allow us to understand the systematic changes in structure and electronic state that accompany the changes in the redox state.