Isolation of monomeric copper(<scp>ii</scp>) phenolate selenoether complexes using chelating <i>ortho</i>-bisphenylselenide-phenolate ligands and their electrocatalytic hydrogen gas evolution activity

Upadhyay, Aditya; Meena, Harshita; Jha, Raushan Kumar; Kanika,; Kumar, Sangit

doi:10.1039/d2dt00678b

Cited by 10 publications

(9 citation statements)

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“…Redox-active ligands are of special interest in HER because the ligand can act as an electron reservoir and facilitate two-electron activity with earth-abundant, cost-efficient, first-row transition metals in molecular catalysts. − For several years, we and others have evaluated Zn, , Cu, − Ni, − Pd, and Co , complexes with redox-active bis-thiosemicarbazone (BTSC) ligands (Figure ) as electrocatalysts for the HER. The highly modular nature of BTSCs allows tuning of ligand electronics and basicity.…”

Section: Introductionmentioning

confidence: 99%

Ligand-Centered Hydrogen Evolution with Ni(II) and Pd(II)DMTH

et al. 2022

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In this study, we report a pair of electrocatalysts for the hydrogen evolution reaction (HER) based on the noninnocent ligand diacetyl-2-(4-methyl-3-thiosemicarbazone)-3-(2-pyridinehydrazone) (H 2 DMTH, H 2 L 1 ). The neutral complexes NiL 1 and PdL 1 were synthesized and characterized by spectroscopic and electrochemical methods. The complexes contain a non-coordinating, basic hydrazino nitrogen that is protonated during the HER. The pK a of this nitrogen was determined by spectrophotometric titration in acetonitrile to be 12.71 for NiL 1 and 13.03 for PdL 1 . Cyclic voltammograms of both NiL 1 and PdL 1 in acetonitrile exhibit diffusion-controlled, reversible ligand-centered events at −1.83 and −1.79 V (vs ferrocenium/ferrocene) for NiL 1 and PdL 1 , respectively. A quasireversible, ligand-centered event is observed at −2.43 and −2.34 V for NiL 1 and PdL 1 , respectively. The HER activity in acetonitrile was evaluated using a series of neutral and cationic acids for each catalyst. Kinetic isotope effect (KIE) studies suggest that the precatalytic event observed is associated with a proton-coupled electron transfer step. The highest turnover frequency values observed were 6150 s −1 at an overpotential of 0.74 V for NiL 1 and 8280 s −1 at an overpotential of 0.44 V for PdL 1 . Density functional theory (DFT) computations suggest both complexes follow a ligand-centered HER mechanism where the metals remain in the +2 oxidation state.

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Section: Introductionmentioning

confidence: 99%

Ligand-Centered Hydrogen Evolution with Ni(II) and Pd(II)DMTH

et al. 2022

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“…It is reported that transition metal ions can form complexes with organoselenium compounds. 26,27 The fact that visible light may promote the breaking of the Se-Se bond has been reported. 28 These reports and the previous experimental research results provide an important basis for us to speculate about mechanism of the threecomponent reaction of olefins, indoles, and diselenides.…”

Section: S C H E M E 3 Investigation Of Indoles With Various Substitu...mentioning

confidence: 99%

Blue LED light‐promoted CuCl₂‐catalyzed three component reaction of styrenes, indoles, and diselenides

Yin,

Wang,

Shen

et al. 2023

Applied Organom Chemis

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A three‐component reaction of olefins, indoles, and diaryl diselenides catalyzed by copper chloride under irradiation of blue LED light is disclosed. Various diaryl diselenides including diheteroaryl diselenides are suitable for this bifunctionalization of olefins. This protocol provides 26 examples of β‐(hetero)arylselenyl indoles in 60%–87% yields. The proposed mechanism involves activation of diaryl diselenides by coordination with copper chloride, generation of arylselenium cations by heterolysis of activated diaryl diselenides, electrophilic addition of arylselenium cations to styrenes, and then Friedel–Crafts‐type alkylation at the 3‐position of NH‐indoles.

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“…It is presumably due to difficulty in the preparation of chelating diaryl selenide ligands. Recently, we have isolated a series of air-stable bimetallic zinc selenolate 47 and monomeric copper phenolate selenoether complexes 48 for the electrocatalytic HER by ligand-centered and ligand-assisted pathways, respectively. In order to obtain efficient selenium-containing electrocatalysts, we continued our work on the isolation of ligand-based stable metal–selenium electrocatalysts.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of cobalt(ii) phenolate selenoether complexes to mimic hydrogenase-like activity for hydrogen gas production

et al. 2023

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Isolation of monomeric copper(ii) phenolate selenoether complexes using chelating ortho-bisphenylselenide-phenolate ligands and their electrocatalytic hydrogen gas evolution activity

Abstract: A series of novel copper(II) phenolate selenoether complexes have been synthesized and structurally characterized for the first time from copper(I)phenanthroline and various substituted ortho-bisphenylselenide-phenol chelating ligands. The synthesized complex exhibit...

Cited by 10 publications

References 42 publications

Ligand-Centered Hydrogen Evolution with Ni(II) and Pd(II)DMTH

Ligand-Centered Hydrogen Evolution with Ni(II) and Pd(II)DMTH

Blue LED light‐promoted CuCl₂‐catalyzed three component reaction of styrenes, indoles, and diselenides

Synthesis of cobalt(ii) phenolate selenoether complexes to mimic hydrogenase-like activity for hydrogen gas production

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Isolation of monomeric copper(ii) phenolate selenoether complexes using chelating ortho-bisphenylselenide-phenolate ligands and their electrocatalytic hydrogen gas evolution activity

Abstract: A series of novel copper(II) phenolate selenoether complexes have been synthesized and structurally characterized for the first time from copper(I)phenanthroline and various substituted ortho-bisphenylselenide-phenol chelating ligands. The synthesized complex exhibit...

Cited by 10 publications

References 42 publications

Ligand-Centered Hydrogen Evolution with Ni(II) and Pd(II)DMTH

Ligand-Centered Hydrogen Evolution with Ni(II) and Pd(II)DMTH

Blue LED light‐promoted CuCl2‐catalyzed three component reaction of styrenes, indoles, and diselenides

Synthesis of cobalt(ii) phenolate selenoether complexes to mimic hydrogenase-like activity for hydrogen gas production

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Blue LED light‐promoted CuCl₂‐catalyzed three component reaction of styrenes, indoles, and diselenides