Mn2(CO)6(μ-mbi)2 as a precursor for mono- and polynuclear complexes containing the 2-mercaptobenzimidazolate (mbi) ligand

Abedin, Tareque S. M.; Moni, Md. Rassel; Ghosh, Shishir; Tocher, Derek A.; Mobin, Shaikh M.; Kabir, Shariff E.

doi:10.1016/j.poly.2018.06.039

Cited by 9 publications

(3 citation statements)

References 47 publications

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“…Complexes 1–4 were characterized by a combination of different spectroscopic techniques together with single crystal X‐ray diffraction studies for complexes 1 , 3 and ligand L 1 . Since the X‐ray structures for complexes 1 and 3 have been reported previously, only the salient features of the structures are discussed below ,…”

Section: Resultssupporting

confidence: 89%

“…The effective atomic number (EAN) rule (defined as the noble gas atomic number achieved by metals via binding with ligands for the formation of a stable metal complex) was followed by each manganese without taking into account the metal‐metal bond and considering that the thiolate ligands serve as 5‐electron donors. The spectroscopic data for complexes 1 and 3 matched well with that reported by Kabir et al ,…”

Section: Resultsmentioning

confidence: 99%

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Dinuclear Manganese Carbonyl Complexes: Electrocatalytic Reduction of Protons to Dihydrogen

2019

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Studies on Mn complexes as electrocatalysts for proton reduction are limited. Mostly Mn complexes have been investigated for CO 2 activation. Hence, hydrogen production by three Mn complexes [(Mn(CO) 3 (μ-SN 2 C 7 H 5 )) 2 ] 1, [(Mn(CO) 3 (μ-S 2 NC 7 H 4 )) 2 ] 3 and [Mn 2 (CO) 7 (μ-S 2 NC 7 H 4 ) 2 ] 4 is reported in the paper. The complexes 1, 3 and 4 effectively catalyzed electro-chemical proton reduction in CH 3 CN with trifluoroacetic acid (TFA) as the proton source. Complexes 1, 3 and 4 displayed turnover frequency (TOF / s À 1 ) (overpotential, η / V) of 358 (0.83), 111 (0.79) and 102 (0.77), respectively for the catalytic process.

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Section: Resultssupporting

confidence: 89%

Section: Resultsmentioning

confidence: 99%

Dinuclear Manganese Carbonyl Complexes: Electrocatalytic Reduction of Protons to Dihydrogen

2019

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“…The experimental and computational details are discussed in detail in the electronic supporting information (ESI). (Abedin et al, 2018). All the complexes 1-4 were characterized using different spectroscopic techniques such as FTIR, 1 H, and 31 P NMR spectroscopy and MS spectrometry (see Supplementary Figures S1-S7, ESI).…”

Section: Methodsmentioning

confidence: 99%

Mononuclear manganese complexes as hydrogen evolving catalysts

Kaim

Joshi²,

Stein³

et al. 2022

Front. Chem.

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Molecular hydrogen (H2) is one of the pillars of future non-fossil energy supply. In the quest for alternative, non-precious metal catalysts for hydrogen generation to replace platinum, biological systems such as the enzyme hydrogenase serve as a blueprint. By taking inspiration from the bio-system, mostly nickel- or iron-based catalysts were explored so far. Manganese is a known oxygen-reducing catalyst but has received much less attention for its ability to reduce protons in acidic media. Here, the synthesis, characterization, and reaction mechanisms of a series of four mono-nuclear Mn(I) complexes in terms of their catalytic performance are reported. The effect of the variation of equatorial and axial ligands in their first and second coordination spheres was assessed pertaining to their control of the turnover frequencies and overpotentials. All four complexes show reactivity and reduce protons in acidic media to release molecular hydrogen H2. Quantum chemical studies were able to assign and interpret spectral characterizations from UV–Vis and electrochemistry and rationalize the reaction mechanism. Two feasible reaction mechanisms of electrochemical (E) and protonation (C) steps were compared. Quantum chemical studies can assign peaks in the cyclic voltammetry to structural changes of the complex during the reaction. The first one-electron reduction is essential to generate an open ligand-based site for protonation. The distorted octahedral Mn complexes possess an inverted second one-electron redox potential which is a pre-requisite for a swift and facile release of molecular hydrogen. This series on manganese catalysts extends the range of elements of the periodic table which are able to catalyze the hydrogen evolution reaction and will be explored further.

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Hydrogen Evolving Mono‐Nuclear Manganese Complexes with Carefully Positioned Pyridine Base Ligands

Hussein,

Joshi,

Kaur‐Ghumaan

et al. 2024

ChemCatChem

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Enormous efforts have been made by the scientific community for the development of biomimetic/bioinspired complexes as alternative energy systems to overcome the energy crisis arising from the depletion of non‐renewable energy sources. In this regard, new bioinspired mononuclear Mn(I) carbonyl model complexes fac‐[(Mn(CO)3(κ2‐SN2C7H5)(κ1‐PPh2Py))] 1 and fac‐[(Mn(CO)3(κ2‐S2NC7H4)(κ1‐PPh2Py))] 2 with 2‐mercaptobenzimidazole (N,N) and 2‐mercaptobenzothiazole (S,N) ligands and a N‐based phosphine ligand (PPh2Py) have been synthesized, spectroscopically characterized and evaluated as electro‐catalysts for hydrogen generation. Contrary to similar mono‐nuclear (N,N/S,N)‐Mn‐PPh3 complexes reported earlier by our group, based on DFT calculations, it has been shown that the pyridine ring of the PPh2Py ligand placed in an axial position in the coordination sphere of the Mn(I) complexes provides a first site for protonation. Both the molecular complexes were tested as electrocatalysts for hydrogen generation in CH3CN. Complexes 1 and 2 effectively catalyzed electrochemical proton reduction with acetic acid as the proton source and displayed a turnover frequency (TOF / s‐1; O.P., η /V) of 610; 1.02 and 615; 1.12, respectively, for the electro‐catalytic process.

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Mn2(CO)6(μ-mbi)2 as a precursor for mono- and polynuclear complexes containing the 2-mercaptobenzimidazolate (mbi) ligand

Cited by 9 publications

References 47 publications

Dinuclear Manganese Carbonyl Complexes: Electrocatalytic Reduction of Protons to Dihydrogen

Dinuclear Manganese Carbonyl Complexes: Electrocatalytic Reduction of Protons to Dihydrogen

Mononuclear manganese complexes as hydrogen evolving catalysts

Hydrogen Evolving Mono‐Nuclear Manganese Complexes with Carefully Positioned Pyridine Base Ligands

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