A novel nonheme manganese(<scp>ii</scp>) complex for (electro) catalytic oxidation of water

Narulkar, Dattaprasad D.; Devulapally, Koteshwar; Kumar, Udit; Dhuri, Sunder N.; Dhavale, Vishal M.; Vardhaman, Anil Kumar; Giribabu, Lingamallu

doi:10.1039/d0se00232a

Cited by 4 publications

(3 citation statements)

References 46 publications

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“…However, anionic donors are not strictly necessary, as evidenced by the report from Smith of a dicationic mononuclear manganese pyridinophane complex (Figure 2C) that is effective in electrocatalytic water oxidation (TON = 16-24) [23]. Scattered examples of other mononuclear manganese complexes that are competent precatalysts for electrocatalytic water oxidation, often supported by poly-dentate nitrogen donor ligands, have been reported in the last few years, although in some cases, the nature of the active catalyst in the system is not yet clear [24][25][26][27].…”

Section: Introductionmentioning

confidence: 91%

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Synthesis and Characterization of Bipyridyl-(Imidazole)n Mn(II) Compounds and Their Evaluation as Potential Precatalysts for Water Oxidation

Mu,

Gaynor,

McIntyre

et al. 2023

Molecules

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Metalloenzymes make extensive use of manganese centers for oxidative catalysis, including water oxidation; the need to develop improved synthetic catalysts for these processes has long motivated the development of bioinspired manganese complexes. Herein, we report a series of bpy-(imidazole)n (n = 1 or 2) (bpy = 2,2′-bipyridyl) ligands and their Mn2+ complexes. Four Mn2+ complexes are structurally characterized using single-crystal X-ray diffraction, revealing different tridentate and tetradentate ligand coordination modes. Cyclic voltammetry of the complexes is consistent with ligand-centered reductions and metal-centered oxidations, and UV-vis spectroscopy complemented by TD-DFT calculations shows primarily ligand-centered transitions with minor contributions from charge-transfer type transitions at higher energies. In solution, ESI-MS studies provide evidence for ligand reorganization, suggesting complex speciation behavior. The oxidation of the complexes in the presence of water is probed using cyclic voltammetry, but the low stability of the complexes in aqueous solution leads to decomposition and precludes their ultimate application as aqueous electrocatalysts. Possible reasons for the low stability and suggestions for improvement are discussed.

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Section: Introductionmentioning

confidence: 91%

“…Molecules 2023, 28, x FOR PEER REVIEW 3 of 26 oxidation, often supported by polydentate nitrogen donor ligands, have been reported in the last few years, although in some cases, the nature of the active catalyst in the system is not yet clear [24][25][26][27].…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Characterization of Bipyridyl-(Imidazole)n Mn(II) Compounds and Their Evaluation as Potential Precatalysts for Water Oxidation

Mu,

Gaynor,

McIntyre

et al. 2023

Molecules

View full text Add to dashboard Cite

show abstract

“…[26][27][28][29][30][31][32][33][34][35][36][37] However, they are mainly utilized as the catalysts for chemical/light driven water oxidation and only a few of them have been reported for electrochemical water oxidation. [38][39][40][41][42][43][44] Therefore, the development of Mn based WOCs with low overpotential and high catalytic efficiency is of great significance.…”

Section: Introductionmentioning

confidence: 99%

Electrochemical water oxidation using a stable water-soluble mononuclear manganese clathrochelate

Zheng¹,

Liang²,

Dai³

et al. 2023

New J. Chem.

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Water Oxidation by a Neoteric Dinuclear Mn(II) Electrocatalyst in Aqueous Medium

Raj

Padhi

2022

Eur J Inorg Chem

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The employment of manganese complexes towards electrocatalytic water oxidation has gained immense interest among the scientific communities. In this present study, the reaction of Mn(CH 3 COO) 2 •4H 2 O with the novel ligand (2-([2,2':6',2"-terpyridin]-4'-yl)quinoline-8-ol) (8hq-tpy) affords a dinuclear manganese complex, [Mn II (8hq-tpy)(H 2 O)] 2 (PF 6 ) 2 (Mn 1). Various spectroscopic techniques have been implemented for characterization purposes, and Mn 1 is employed as electrocatalysts towards water oxidation catalysis in the aqueous medium. Electrocatalytic responses in the aqueous medium at pH 6.0 lead to the electrodeposition of heterogeneous species (MnO X ) which enables the oxidation event at an applied potential of 1.24 V vs. NHE with O 2 liberation of 50.2 μmol/L. The XPS analysis performed after executing bulk electrolysis, provide evidence for the generation of Mn IV = O as the active species formed by the catalyst precursor complex Mn 1, contributing to O 2 evolution during the electrocatalytic water oxidation process.

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A novel nonheme manganese(ii) complex for (electro) catalytic oxidation of water

Abstract: A nonheme single-metal-site Mn-complex i.e. [Mn(N3Py2)H2O] (ClO4)2; where N3Py2 = N,N′-dimethyl-N-(2-(methyl(pyridin-2-ylmethyl)amino)-ethyl-N′-(pyridin-2-ylmethyl)ethane-1,2-diamine) displays electrochemical water oxidation ability in a wide pH range.

Cited by 4 publications

References 46 publications

Synthesis and Characterization of Bipyridyl-(Imidazole)n Mn(II) Compounds and Their Evaluation as Potential Precatalysts for Water Oxidation

Synthesis and Characterization of Bipyridyl-(Imidazole)n Mn(II) Compounds and Their Evaluation as Potential Precatalysts for Water Oxidation

Electrochemical water oxidation using a stable water-soluble mononuclear manganese clathrochelate

Water Oxidation by a Neoteric Dinuclear Mn(II) Electrocatalyst in Aqueous Medium

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