Redox properties of a bipyrimidine-bridged dinuclear ruthenium(II) complex

Tomoya Ishizuka, Masaki Itogawa, Hinatsu Shimomura, Yoshihito Shiota, Hiroaki Kotani, Kazunari Yoshizawa, Takahiko Kojima

Research output: Contribution to journalArticlepeer-review

Abstract

A dinuclear RuII complex, [{RuIICl(MeBPA)}2(μ-bpm)](PF6)2 (1), exhibited three reversible redox waves at –0.75, +0.91 and +1.15 V vs Ag/AgCl in acetone at –60 °C. The former wave can be assigned to the 1e-reduction process of the bridging bpm ligand and the latter two are assigned to the stepwise 1e-oxidation processes of the two Ru centers. Electrochemical oxidation of 1 afforded a “class I” mixed-valence (MV) state, in which the charge localizes on one of the two Ru centers. On the other hand, electrochemical 1e-reduction of 1 predominantly proceeds on the bridging bpm ligand. The valence-localized MV state should be derived from a largely distorted structure of the RuII site to reduce the π-back bonding from a filled RuII dπ orbital to the bpm ligand as suggested by DFT calculations.

Original languageEnglish
Article number108150
JournalInorganic Chemistry Communications
Volume120
DOIs
Publication statusPublished - Oct 2020

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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