Transition metal-mediated O–O bond formation and activation in chemistry and biology

Zhang, Xue Peng; Chandra, Anirban; Lee, Yong Min; Cao, Rui; Ray, Kallol; Nam, Wonwoo

doi:10.1039/d0cs01456g

Cited by 142 publications

(110 citation statements)

References 35 publications

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“…In Figure 5b the 3D plots of the electron density difference Δρ(x,y,z) between the three adducts and their corresponding, noninteracting fragments are shown (see the SI, Section 8.1). The fragments defined here are the alkali metal cation (M + ) and the [LCu 2 O 2 ] + complex (1). Figure 5b clearly shows that, upon interaction, the peroxo unit is strongly polarized toward the cation to different extents on going from 1•K + to 1•Li + .…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Modulation of a μ-1,2-Peroxo Dicopper(II) Intermediate by Strong Interaction with Alkali Metal Ions

et al. 2021

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The properties of metal/dioxygen species, which are key intermediates in oxidation catalysis, can be modulated by interaction with redox-inactive Lewis acids, but structural information about these adducts is scarce. Here we demonstrate that even mildly Lewis acidic alkali metal ions, which are typically viewed as innocent “spectators”, bind strongly to a reactive cis-peroxo dicopper(II) intermediate. Unprecedented structural insight has now been obtained from X-ray crystallographic characterization of the “bare” CuII 2(μ-η1:η1-O2) motif and its Li+, Na+, and K+ complexes. UV–vis, Raman, and electrochemical studies show that the binding persists in MeCN solution, growing stronger in proportion to the cation’s Lewis acidity. The affinity for Li+ is surprisingly high (∼70 × 104 M–1), leading to Li+ extraction from its crown ether complex. Computational analysis indicates that the alkali ions influence the entire Cu-OO-Cu core, modulating the degree of charge transfer from copper to dioxygen. This induces significant changes in the electronic, magnetic, and electrochemical signatures of the Cu2O2 species. These findings have far-reaching implications for analyses of transient metal/dioxygen intermediates, which are often studied in situ, and they may be relevant to many (bio)chemical oxidation processes when considering the widespread presence of alkali cations in synthetic and natural environments.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Modulation of a μ-1,2-Peroxo Dicopper(II) Intermediate by Strong Interaction with Alkali Metal Ions

et al. 2021

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“…To realize the rational design of HER electrocatalysts, elucidating the effects of various structural components on HER is of fundamental and practical significance. Molecular complexes have the benefits for studying structure‐function relationships [26–29] . Recent efforts have led to the identification of a variety of molecular complexes, made of earth‐abundant transition metals, as active HER electrocatalysts [30–51] .…”

Section: Introductionmentioning

confidence: 99%

“…Molecular complexes have the benefits for studying structure-function relationships. [26][27][28][29] Recent efforts have led to the identification of a variety of molecular complexes, made of earth-abundant transition metals, as active HER electrocatalysts. By studying these complexes, it is learned that introducing proton relays [31,52,53] and 2 nd sphere redox-active groups [54] can boost electrocatalytic HER.…”

Section: Introductionmentioning

confidence: 99%

Through‐Space Electrostatic Effects of Positively Charged Substituents on the Hydrogen Evolution Reaction

et al. 2022

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Elucidating the effects of various structural components on energy-related small molecule activation is of fundamental and practical significance. Herein the inhibition effect of positively charged substituents on the hydrogen evolution reaction (HER) was reported. With the use of Cu porphyrins 1-5 containing different numbers and locations of positively charged substituents, it was demonstrated that their electrocatalytic HER activities significantly decreased when more cationic units were located close to the Cu ion: the i cat /i p (i cat is the catalytic peak current, i p is the one-electron reduction peak current) value decreased from 38 with zero cationic unit to 15 with four closely located cationic units. Inspired by this result, Cu porphyrin 6, with four meso-phenyl groups each bearing a negatively charged para-sulfonic substituent, was designed. With these anionic units, 6 outperformed the other Cu porphyrins for electrocatalytic HER under the same conditions.

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“…Their efficiency is one key towards the high efficiency of H 2 generation and utilization [6–10] . Therefore, the viability of a hydrogen society also depends on developing efficient ORR and OER electrocatalysts [4, 11–14] . In addition, rechargeable metal‐air batteries require bifunctional electrocatalysts for ORR and OER [12, 15, 16] .…”

Section: Figurementioning

confidence: 99%

Metal‐Corrole‐Based Porous Organic Polymers for Electrocatalytic Oxygen Reduction and Evolution Reactions

et al. 2022

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Integrating molecular catalysts into designed frameworks often enables improved catalysis. Compared with porphyrin‐based frameworks, metal‐corrole‐based frameworks have been rarely developed, although monomeric metal corroles are usually more efficient than porphyrin counterparts for the electrocatalytic oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). We herein report on metal‐corrole‐based porous organic polymers (POPs) as ORR and OER electrocatalysts. M‐POPs (M=Mn, Fe, Co, Cu) were synthesized by coupling metal 10‐phenyl‐5,15‐(4‐iodophenyl)corrole with tetrakis(4‐ethynylphenyl)methane. Compared with metal corrole monomers, M‐POPs displayed significantly enhanced catalytic activity and stability. Co‐POP outperformed other M‐POPs by achieving four‐electron ORR with a half‐wave potential of 0.87 V vs. RHE and reaching 10 mA cm−2 OER current density at 340 mV overpotential. This work is unparalleled to develop and explore metal‐corrole‐based POPs as electrocatalysts.

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Transition metal-mediated O–O bond formation and activation in chemistry and biology

Abstract: O–O bond formation and activation reactions proceed via multi-step reactions in chemistry and biology and involve similar reactive intermediates like metal–oxo/oxyl, metal–superoxo, and/or metal–(hydro)peroxo species.

Cited by 142 publications

References 35 publications

Modulation of a μ-1,2-Peroxo Dicopper(II) Intermediate by Strong Interaction with Alkali Metal Ions

Modulation of a μ-1,2-Peroxo Dicopper(II) Intermediate by Strong Interaction with Alkali Metal Ions

Through‐Space Electrostatic Effects of Positively Charged Substituents on the Hydrogen Evolution Reaction

Metal‐Corrole‐Based Porous Organic Polymers for Electrocatalytic Oxygen Reduction and Evolution Reactions

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