BIOMAT Database Logo BIOMAT Database Logo

Fundamental electron-transfer and proton-coupled electron-transfer properties of Ru(iv)-oxo complexes. 2019

Hiroaki Kotani, and Hinatsu Shimomura, and Momoka Horimoto, and Tomoya Ishizuka, and Yoshihito Shiota, and Kazunari Yoshizawa, and Sachiko Yanagisawa, and Yuka Kawahara-Nakagawa, and Minoru Kubo, and Takahiko Kojima
Department of Chemistry, Graduate School of Pure and Applied Sciences, University of Tsukuba and CREST (JST), 1-1-1 Tennoudai, Tsukuba, Ibaraki 305-8571, Japan. kojima@chem.tsukuba.ac.jp.

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.

UI MeSH Term Description Entries

Related Publications

Hiroaki Kotani, and Hinatsu Shimomura, and Momoka Horimoto, and Tomoya Ishizuka, and Yoshihito Shiota, and Kazunari Yoshizawa, and Sachiko Yanagisawa, and Yuka Kawahara-Nakagawa, and Minoru Kubo, and Takahiko Kojima
Fundamental electron-transfer properties of non-heme oxoiron(IV) complexes.
January 2008, Journal of the American Chemical Society,
Hiroaki Kotani, and Hinatsu Shimomura, and Momoka Horimoto, and Tomoya Ishizuka, and Yoshihito Shiota, and Kazunari Yoshizawa, and Sachiko Yanagisawa, and Yuka Kawahara-Nakagawa, and Minoru Kubo, and Takahiko Kojima
Electron Transfer Reactivity of the Aqueous Iron(IV)-Oxo Complex. Outer-Sphere vs Proton-Coupled Electron Transfer.
July 2016, Inorganic chemistry,
Hiroaki Kotani, and Hinatsu Shimomura, and Momoka Horimoto, and Tomoya Ishizuka, and Yoshihito Shiota, and Kazunari Yoshizawa, and Sachiko Yanagisawa, and Yuka Kawahara-Nakagawa, and Minoru Kubo, and Takahiko Kojima
Thermodynamics of Proton-Coupled Electron Transfer at Tricopper μ-Oxo/Hydroxo/Aqua Complexes.
May 2024, Journal of the American Chemical Society,
Hiroaki Kotani, and Hinatsu Shimomura, and Momoka Horimoto, and Tomoya Ishizuka, and Yoshihito Shiota, and Kazunari Yoshizawa, and Sachiko Yanagisawa, and Yuka Kawahara-Nakagawa, and Minoru Kubo, and Takahiko Kojima
Proton-promoted oxygen atom transfer vs proton-coupled electron transfer of a non-heme iron(IV)-oxo complex.
February 2012, Journal of the American Chemical Society,
Hiroaki Kotani, and Hinatsu Shimomura, and Momoka Horimoto, and Tomoya Ishizuka, and Yoshihito Shiota, and Kazunari Yoshizawa, and Sachiko Yanagisawa, and Yuka Kawahara-Nakagawa, and Minoru Kubo, and Takahiko Kojima
Oxygen Atom Transfer, Coupled Electron-Proton Transfer, and Correlated Electron-Nucleophile Transfer Reactions of Oxomolybdenum(IV) and Dioxomolybdenum(VI) Complexes.
February 1996, Inorganic chemistry,
Hiroaki Kotani, and Hinatsu Shimomura, and Momoka Horimoto, and Tomoya Ishizuka, and Yoshihito Shiota, and Kazunari Yoshizawa, and Sachiko Yanagisawa, and Yuka Kawahara-Nakagawa, and Minoru Kubo, and Takahiko Kojima
Proton-coupled electron transfer with photoexcited metal complexes.
July 2013, Accounts of chemical research,
Hiroaki Kotani, and Hinatsu Shimomura, and Momoka Horimoto, and Tomoya Ishizuka, and Yoshihito Shiota, and Kazunari Yoshizawa, and Sachiko Yanagisawa, and Yuka Kawahara-Nakagawa, and Minoru Kubo, and Takahiko Kojima
Effects of proton acceptors on formation of a non-heme iron(IV)-oxo complex via proton-coupled electron transfer.
March 2013, Inorganic chemistry,
Hiroaki Kotani, and Hinatsu Shimomura, and Momoka Horimoto, and Tomoya Ishizuka, and Yoshihito Shiota, and Kazunari Yoshizawa, and Sachiko Yanagisawa, and Yuka Kawahara-Nakagawa, and Minoru Kubo, and Takahiko Kojima
Contrasting effects of axial ligands on electron-transfer versus proton-coupled electron-transfer reactions of nonheme oxoiron(IV) complexes.
January 2010, Chemistry (Weinheim an der Bergstrasse, Germany),
Hiroaki Kotani, and Hinatsu Shimomura, and Momoka Horimoto, and Tomoya Ishizuka, and Yoshihito Shiota, and Kazunari Yoshizawa, and Sachiko Yanagisawa, and Yuka Kawahara-Nakagawa, and Minoru Kubo, and Takahiko Kojima
Concerted proton-electron transfer reactions of manganese-hydroxo and manganese-oxo complexes.
August 2020, Chemical communications (Cambridge, England),
Hiroaki Kotani, and Hinatsu Shimomura, and Momoka Horimoto, and Tomoya Ishizuka, and Yoshihito Shiota, and Kazunari Yoshizawa, and Sachiko Yanagisawa, and Yuka Kawahara-Nakagawa, and Minoru Kubo, and Takahiko Kojima
Proton-coupled electron-transfer oxidation of phenols by hexachloroiridate(IV).
December 2008, Inorganic chemistry,
Copied contents to your clipboard!