Proton-induced tuning of metal-metal communication in rack-type dinuclear Ru complexes containing benzimidazolyl moieties

Katsuaki Kobayashi, Masamichi Ishikubo, Katsuhiko Kanaizuka, Keiko Kosuge, Shigeyuki Masaoka, Ken Sakai, Koichi Nozaki, Masa Aki Haga

研究成果: Contribution to journalArticle査読

19 被引用数 (Scopus)

抄録

Ru complexes bearing a bis-tridentate benzimidazolyl ligand have been synthesized. The dinuclear ones act as a bibasic acid with pKa1=4.36 and pKa2=5.90. The protonated form of the dinuclear complex exhibited two one-electron oxidations at +0.91 and +1.02V versus the ferrocenium/ ferrocene (Fc/Fc+) couple (the potential difference (ΔE)=0.11V), but the di-deprotonated form showed two waves at +0.50 and +0.58V versus Fc/Fc+ (ΔE=0.08V). Since the potential difference between two waves reflects the strength of the metal-metal interaction, the deprotonation of the benzimidazole moieties in the complexes weakened the Ru-Ru communication. The degree of electronic coupling between two metal centers, estimated from the intervalence charge transfer (IVCT) band, was greater for the protonated form. DFT calculations for the protonated and deprotonated forms of the dinuclear complex suggest that the RuII-L(H2) π* interaction plays a key role in the Ru-Ru interaction.

本文言語英語
ページ(範囲)6954-6963
ページ数10
ジャーナルChemistry - A European Journal
17
25
DOI
出版ステータス出版済み - 6 14 2011

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Organic Chemistry

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