Three Distinct Redox States of an Oxo-Bridged Dinuclear Ruthenium Complex

Masaki Yoshida, Mio Kondo, Toshikazu Nakamura, Ken Sakai, Shigeyuki Masaoka

研究成果: Contribution to journalArticle査読

15 被引用数 (Scopus)

抄録

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 RuII,III2, RuIII,III2, and RuIII,IV2, 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 Ru O 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, [RuIIIORuIV]5+ and [RuIIORuIII]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.

本文言語英語
ページ(範囲)11519-11523
ページ数5
ジャーナルAngewandte Chemie - International Edition
53
43
DOI
出版ステータス出版済み - 10 1 2014

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)

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