TY - JOUR
T1 - Redox properties of a bipyrimidine-bridged dinuclear ruthenium(II) complex
AU - Ishizuka, Tomoya
AU - Itogawa, Masaki
AU - Shimomura, Hinatsu
AU - Shiota, Yoshihito
AU - Kotani, Hiroaki
AU - Yoshizawa, Kazunari
AU - Kojima, Takahiko
N1 - Funding Information:
This work was supported by Grants-in-Aids (Nos. 15H00915 and 17H03027 to T. K.) from Japan Society of Science and Technology ( JSPS ).
Publisher Copyright:
© 2020 Elsevier B.V.
PY - 2020/10
Y1 - 2020/10
N2 - 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.
AB - 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.
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U2 - 10.1016/j.inoche.2020.108150
DO - 10.1016/j.inoche.2020.108150
M3 - Article
AN - SCOPUS:85089109647
SN - 1387-7003
VL - 120
JO - Inorganic Chemistry Communications
JF - Inorganic Chemistry Communications
M1 - 108150
ER -