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

Research output: Contribution to journalArticle

Abstract

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.

Original languageEnglish
Pages (from-to)13154-13161
Number of pages8
JournalDalton Transactions
Volume48
Issue number35
DOIs
Publication statusPublished - Jan 1 2019

Fingerprint

Protons
Electrons
Discrete Fourier transforms
Oxidation

All Science Journal Classification (ASJC) codes

  • Inorganic Chemistry

Cite this

Fundamental electron-transfer and proton-coupled electron-transfer properties of Ru(iv)-oxo complexes. / Kotani, Hiroaki; Shimomura, Hinatsu; Horimoto, Momoka; Ishizuka, Tomoya; Shiota, Yoshihito; Yoshizawa, Kazunari; Yanagisawa, Sachiko; Kawahara-Nakagawa, Yuka; Kubo, Minoru; Kojima, Takahiko.

In: Dalton Transactions, Vol. 48, No. 35, 01.01.2019, p. 13154-13161.

Research output: Contribution to journalArticle

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, vol. 48, no. 35, pp. 13154-13161. https://doi.org/10.1039/c9dt02734c
Kotani, Hiroaki ; Shimomura, Hinatsu ; Horimoto, Momoka ; Ishizuka, Tomoya ; Shiota, Yoshihito ; Yoshizawa, Kazunari ; Yanagisawa, Sachiko ; Kawahara-Nakagawa, Yuka ; Kubo, Minoru ; Kojima, Takahiko. / Fundamental electron-transfer and proton-coupled electron-transfer properties of Ru(iv)-oxo complexes. In: Dalton Transactions. 2019 ; Vol. 48, No. 35. pp. 13154-13161.
@article{fd659882387d4e84ae3b6b21761670b0,
title = "Fundamental electron-transfer and proton-coupled electron-transfer properties of Ru(iv)-oxo complexes",
abstract = "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.",
author = "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",
year = "2019",
month = "1",
day = "1",
doi = "10.1039/c9dt02734c",
language = "English",
volume = "48",
pages = "13154--13161",
journal = "Dalton Transactions",
issn = "1477-9226",
publisher = "Royal Society of Chemistry",
number = "35",

}

TY - JOUR

T1 - Fundamental electron-transfer and proton-coupled electron-transfer properties of Ru(iv)-oxo complexes

AU - Kotani, Hiroaki

AU - Shimomura, Hinatsu

AU - Horimoto, Momoka

AU - Ishizuka, Tomoya

AU - Shiota, Yoshihito

AU - Yoshizawa, Kazunari

AU - Yanagisawa, Sachiko

AU - Kawahara-Nakagawa, Yuka

AU - Kubo, Minoru

AU - Kojima, Takahiko

PY - 2019/1/1

Y1 - 2019/1/1

N2 - 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.

AB - 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.

UR - http://www.scopus.com/inward/record.url?scp=85071996277&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85071996277&partnerID=8YFLogxK

U2 - 10.1039/c9dt02734c

DO - 10.1039/c9dt02734c

M3 - Article

C2 - 31328211

AN - SCOPUS:85071996277

VL - 48

SP - 13154

EP - 13161

JO - Dalton Transactions

JF - Dalton Transactions

SN - 1477-9226

IS - 35

ER -