Amphoteric reactivity of metal–oxygen complexes in oxidation reactions

Muniyandi Sankaralingam; Yong Min Lee; Wonwoo Nam; Shunichi Fukuzumi

doi:10.1016/j.ccr.2018.03.003

Amphoteric reactivity of metal–oxygen complexes in oxidation reactions

Muniyandi Sankaralingam, Yong Min Lee, Wonwoo Nam, Shunichi Fukuzumi

Chemistry & Nanoscience

Research output: Contribution to journal › Review article › peer-review

73 Scopus citations

Abstract

Mononuclear metal–oxygen species, such as metal-superoxo, -peroxo, -hydroperoxo and -oxo complexes, are key intermediates involved in dioxygen activation and oxidation reactions catalyzed by a variety of metalloenzymes and their biomimetic compounds. Dioxygen is an electrophile or electron acceptor, but not a nucleophile or electron donor. However, when dioxygen is bound to metal complexes and metal–oxygen species are formed, such as metal-superoxo, -peroxo, -hydroperoxo, alkylperoxo, and -oxo complexes, the metal–oxygen intermediates react as nucleophiles and electron donors as well as electrophiles and electron acceptors. This review is intended to focus on such an amphoteric reactivity of the metal–oxygen complexes in electrophilic and nucleophilic reactions. Both the electronic and steric effects of the ligands have finely tuned the reactivity of metal–oxygen complexes in both the electrophilic and nucleophilic reactions. The amphoteric reactivity of metal–oxygen complexes can also be tuned by binding of redox-inactive metal ions acting as Lewis acids and also by binding of Brønsted acids.

Original language	English
Pages (from-to)	41-59
Number of pages	19
Journal	Coordination Chemistry Reviews
Volume	365
DOIs	https://doi.org/10.1016/j.ccr.2018.03.003
State	Published - 15 Jun 2018

Bibliographical note

Funding Information:
The authors gratefully acknowledge the contributions of their collaborators and coworkers mentioned in the cited references, and financial supports by a SENTAN project from JST and JSPS KAKENHI (Grant Numbers 16H02268 to S.F.) from MEXT , Japan and by the NRF of Korea through CRI ( NRF-2012R1A3A2048842 to W.N.), GRL ( NRF-2010-00353 to W.N.), and Basic Science Research Program ( 2017R1D1A1B03029982 to Y.M.L. and 2017R1D1A1B03032615 to S.F.).

Funding Information:
The authors gratefully acknowledge the contributions of their collaborators and coworkers mentioned in the cited references, and financial supports by a SENTAN project from JST and JSPS KAKENHI (Grant Numbers 16H02268 to S.F.) from MEXT, Japan and by the NRF of Korea through CRI (NRF-2012R1A3A2048842 to W.N.), GRL (NRF-2010-00353 to W.N.), and Basic Science Research Program (2017R1D1A1B03029982 to Y.M.L. and 2017R1D1A1B03032615 to S.F.).

Publisher Copyright:
© 2018 Elsevier B.V.

Keywords

Amphoteric reactivity
Electrophilic reactions
Metal–oxygen complexes
Nucleophilic reactions
Oxidation mechanism

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10.1016/j.ccr.2018.03.003

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title = "Amphoteric reactivity of metal–oxygen complexes in oxidation reactions",

abstract = "Mononuclear metal–oxygen species, such as metal-superoxo, -peroxo, -hydroperoxo and -oxo complexes, are key intermediates involved in dioxygen activation and oxidation reactions catalyzed by a variety of metalloenzymes and their biomimetic compounds. Dioxygen is an electrophile or electron acceptor, but not a nucleophile or electron donor. However, when dioxygen is bound to metal complexes and metal–oxygen species are formed, such as metal-superoxo, -peroxo, -hydroperoxo, alkylperoxo, and -oxo complexes, the metal–oxygen intermediates react as nucleophiles and electron donors as well as electrophiles and electron acceptors. This review is intended to focus on such an amphoteric reactivity of the metal–oxygen complexes in electrophilic and nucleophilic reactions. Both the electronic and steric effects of the ligands have finely tuned the reactivity of metal–oxygen complexes in both the electrophilic and nucleophilic reactions. The amphoteric reactivity of metal–oxygen complexes can also be tuned by binding of redox-inactive metal ions acting as Lewis acids and also by binding of Br{\o}nsted acids.",

keywords = "Amphoteric reactivity, Electrophilic reactions, Metal–oxygen complexes, Nucleophilic reactions, Oxidation mechanism",

author = "Muniyandi Sankaralingam and Lee, {Yong Min} and Wonwoo Nam and Shunichi Fukuzumi",

note = "Funding Information: The authors gratefully acknowledge the contributions of their collaborators and coworkers mentioned in the cited references, and financial supports by a SENTAN project from JST and JSPS KAKENHI (Grant Numbers 16H02268 to S.F.) from MEXT , Japan and by the NRF of Korea through CRI ( NRF-2012R1A3A2048842 to W.N.), GRL ( NRF-2010-00353 to W.N.), and Basic Science Research Program ( 2017R1D1A1B03029982 to Y.M.L. and 2017R1D1A1B03032615 to S.F.). Funding Information: The authors gratefully acknowledge the contributions of their collaborators and coworkers mentioned in the cited references, and financial supports by a SENTAN project from JST and JSPS KAKENHI (Grant Numbers 16H02268 to S.F.) from MEXT, Japan and by the NRF of Korea through CRI (NRF-2012R1A3A2048842 to W.N.), GRL (NRF-2010-00353 to W.N.), and Basic Science Research Program (2017R1D1A1B03029982 to Y.M.L. and 2017R1D1A1B03032615 to S.F.). Publisher Copyright: {\textcopyright} 2018 Elsevier B.V.",

year = "2018",

month = jun,

day = "15",

doi = "10.1016/j.ccr.2018.03.003",

language = "English",

volume = "365",

pages = "41--59",

journal = "Coordination Chemistry Reviews",

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T1 - Amphoteric reactivity of metal–oxygen complexes in oxidation reactions

AU - Sankaralingam, Muniyandi

AU - Lee, Yong Min

AU - Nam, Wonwoo

AU - Fukuzumi, Shunichi

N1 - Funding Information: The authors gratefully acknowledge the contributions of their collaborators and coworkers mentioned in the cited references, and financial supports by a SENTAN project from JST and JSPS KAKENHI (Grant Numbers 16H02268 to S.F.) from MEXT , Japan and by the NRF of Korea through CRI ( NRF-2012R1A3A2048842 to W.N.), GRL ( NRF-2010-00353 to W.N.), and Basic Science Research Program ( 2017R1D1A1B03029982 to Y.M.L. and 2017R1D1A1B03032615 to S.F.). Funding Information: The authors gratefully acknowledge the contributions of their collaborators and coworkers mentioned in the cited references, and financial supports by a SENTAN project from JST and JSPS KAKENHI (Grant Numbers 16H02268 to S.F.) from MEXT, Japan and by the NRF of Korea through CRI (NRF-2012R1A3A2048842 to W.N.), GRL (NRF-2010-00353 to W.N.), and Basic Science Research Program (2017R1D1A1B03029982 to Y.M.L. and 2017R1D1A1B03032615 to S.F.). Publisher Copyright: © 2018 Elsevier B.V.

PY - 2018/6/15

Y1 - 2018/6/15

N2 - Mononuclear metal–oxygen species, such as metal-superoxo, -peroxo, -hydroperoxo and -oxo complexes, are key intermediates involved in dioxygen activation and oxidation reactions catalyzed by a variety of metalloenzymes and their biomimetic compounds. Dioxygen is an electrophile or electron acceptor, but not a nucleophile or electron donor. However, when dioxygen is bound to metal complexes and metal–oxygen species are formed, such as metal-superoxo, -peroxo, -hydroperoxo, alkylperoxo, and -oxo complexes, the metal–oxygen intermediates react as nucleophiles and electron donors as well as electrophiles and electron acceptors. This review is intended to focus on such an amphoteric reactivity of the metal–oxygen complexes in electrophilic and nucleophilic reactions. Both the electronic and steric effects of the ligands have finely tuned the reactivity of metal–oxygen complexes in both the electrophilic and nucleophilic reactions. The amphoteric reactivity of metal–oxygen complexes can also be tuned by binding of redox-inactive metal ions acting as Lewis acids and also by binding of Brønsted acids.

AB - Mononuclear metal–oxygen species, such as metal-superoxo, -peroxo, -hydroperoxo and -oxo complexes, are key intermediates involved in dioxygen activation and oxidation reactions catalyzed by a variety of metalloenzymes and their biomimetic compounds. Dioxygen is an electrophile or electron acceptor, but not a nucleophile or electron donor. However, when dioxygen is bound to metal complexes and metal–oxygen species are formed, such as metal-superoxo, -peroxo, -hydroperoxo, alkylperoxo, and -oxo complexes, the metal–oxygen intermediates react as nucleophiles and electron donors as well as electrophiles and electron acceptors. This review is intended to focus on such an amphoteric reactivity of the metal–oxygen complexes in electrophilic and nucleophilic reactions. Both the electronic and steric effects of the ligands have finely tuned the reactivity of metal–oxygen complexes in both the electrophilic and nucleophilic reactions. The amphoteric reactivity of metal–oxygen complexes can also be tuned by binding of redox-inactive metal ions acting as Lewis acids and also by binding of Brønsted acids.

KW - Amphoteric reactivity

KW - Electrophilic reactions

KW - Metal–oxygen complexes

KW - Nucleophilic reactions

KW - Oxidation mechanism

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U2 - 10.1016/j.ccr.2018.03.003

DO - 10.1016/j.ccr.2018.03.003

M3 - Review article

AN - SCOPUS:85044754529

SN - 0010-8545

VL - 365

SP - 41

EP - 59

JO - Coordination Chemistry Reviews

JF - Coordination Chemistry Reviews

ER -

Amphoteric reactivity of metal–oxygen complexes in oxidation reactions

Abstract

Bibliographical note

Keywords

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