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

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

Research output: Contribution to journalArticle

13 Citations (Scopus)

Abstract

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.

Original languageEnglish
Pages (from-to)11519-11523
Number of pages5
JournalAngewandte Chemie - International Edition
Volume53
Issue number43
DOIs
Publication statusPublished - Oct 1 2014

    Fingerprint

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)

Cite this