Fundamental electron-transfer and proton-coupled electron-transfer properties of Ru(iv)-oxo complexes

Hiroaki Kotani, Hinatsu Shimomura, Momoka Horimoto, Tomoya Ishizuka, Yoshihito Shiota, Kazunari Yoshizawa, Sachiko Yanagisawa, Yuka Kawahara-Nakagawa, Minoru Kubo, Takahiko Kojima

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Isolation and characterisation of RuIV(O) complexes were accomplished to investigate their fundamental electron transfer (ET) and proton-coupled ET (PCET) properties. Reorganisation energies (λ) in electron transfer (ET) and proton-coupled ET (PCET) from electron donors to the isolated RuIV(O) complexes have been determined for the first time to be in the range of 1.70-1.88 eV (ET) and 1.20-1.26 eV (PCET). It was suggested that the reduction of the λ values of PCET in comparison with those of ET should be due to the smaller structural change in PCET than that in ET on the basis of DFT calculations on 1 and 1e--reduced 1 in the absence and presence of TFA, respectively. In addition, the smaller λ values for the RuIV(O) complexes than those reported for FeIV(O) and MnIV(O) complexes should be due to the lack of participation of dσ orbitals in the ET and PCET reactions. This is the first example to evaluate fundamental ET and PCET properties of RuIV(O) complexes leading to further understanding of their reactivity in oxidation reactions.

元の言語英語
ページ(範囲)13154-13161
ページ数8
ジャーナルDalton Transactions
48
発行部数35
DOI
出版物ステータス出版済み - 2019

All Science Journal Classification (ASJC) codes

  • Inorganic Chemistry

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    Kotani, H., Shimomura, H., Horimoto, M., Ishizuka, T., Shiota, Y., Yoshizawa, K., Yanagisawa, S., Kawahara-Nakagawa, Y., Kubo, M., & Kojima, T. (2019). Fundamental electron-transfer and proton-coupled electron-transfer properties of Ru(iv)-oxo complexes. Dalton Transactions, 48(35), 13154-13161. https://doi.org/10.1039/c9dt02734c