Molecular Catalysts for Proton Reduction Based on Non‐noble Metals

Elléouet, Catherine; Pétillon, François Y.; Schollhammer, Philippe

doi:10.1002/9783527699087.ch18

Cited by 3 publications

(1 citation statement)

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“…Sustainable hydrogen economy can be achieved by designing systems that can produce hydrogen by photo‐ or electrocatalytic processes from proton or water. Hence, drawing inspiration from nature, wherein the hydrogenase enzymes are known to act as catalysts for the reversible interconversion of protons to dihydrogen with high turnovers {6000–9000 ([FeFe]) and 700 ([NiFe]) mol of H 2 per mol of enzyme per second for HER; 28000 ([FeFe]) and 700 ([NiFe]) mol of H 2 per mol of enzyme per second for HOR}, researchers have been working towards developing selective, efficient, and stable catalysts using more abundant transition metals and various ligand combinations . Complexes of Co, Ni, Fe, have received special attention over the past few decades .…”

Section: Introductionmentioning

confidence: 99%

Manganese Complexes: Hydrogen Generation and Oxidation

Kaim

Kaur‐Ghumaan

2019

Eur J Inorg Chem

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Innovative breakthroughs by designing cheap, sustainable and efficient systems for the conversion and storage of renewable energy sources can help to solve the energy demand. An economically viable way could be the production of hydrogen. Designing noble metal-free catalysts can play an important role in the path towards sustainable hydrogen economy. Nobel metal catalysts are limited by their cost and scalability. In nature, the hydrogenases and photosystem II use iron,

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Section: Introductionmentioning

confidence: 99%

Manganese Complexes: Hydrogen Generation and Oxidation

Kaim

Kaur‐Ghumaan

2019

Eur J Inorg Chem

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Electrocatalytic Proton Reduction by a Cobalt Complex Containing a Proton‐Responsive Bis(alkylimdazole)methane Ligand: Involvement of a C−H Bond in H₂Formation

Ghosh

Vos

Lutz

et al. 2020

Chemistry A European J

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Homogeneous electrocatalytic proton reduction is reported using cobalt complex [1](BF 4) 2 .T his complex comprises two bis(1-methyl-4,5-diphenyl-1H-imidazol-2-yl)methane (HBMIM Ph 2)l igandst hat contain an acidic methylene moiety in their backbone. Upon reduction of [1](BF 4) 2 by either electrochemical or chemical means, one of its HBMIM Ph 2 ligandsu ndergoes deprotonation under the formation of dihydrogen.A ddition of am ild protons ource (acetic acid) to deprotonated complex [2](BF 4)r egenerates protonatedc omplex [1](BF 4) 2 .I np resenceo fa cetic acid in acetonitrile solvent[ 1](BF 4) 2 shows electrocatalytic proton reductionw ith a k obs of % 200 s À1 at an overpotential of 590 mV.M echanistic investigations supported by DFT (BP86) suggest that dihydrogen formation takes place in an intramolecular fashiont hrough the participation of am ethylene CÀHb ond of the HBMIM Ph 2 ligand andaCo II ÀHb ond through formal heterolytic splitting of the latter.T hese findings are of interestt ot he development of responsive ligands formolecular (base)metal(electro)catalysis.

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Tri‐ and Tetra‐Substituted Derivatives of [Fe₂(CO)₆(μ‐dithiolate)] as Novel Dinuclear Platforms Related to the H‐Cluster of [FeFe]H₂ases

et al. 2022

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Novel carbonyl dithiolato diiron complexes [Fe2(CO)6‐xLx(μ‐dithiolate)] (x=3, 4), related to the active site of [FeFe]‐hydrogenases, have been synthesized by photolysis of hexacarbonyl species [Fe2(CO)6(μ‐dithiolate)] (dithiolate={S2(CH2)3} (pdt), {SCH2}2NR with R=iPr (adti−Pr) or Bn (adtBn)). The new compounds were characterized by structural and spectroscopic methods. Variable‐temperature (VT) NMR experiments revealed their fluxionality in solution depending on terminal ligands exchanges and dithiolate bridge motions. Preliminary results on their protonation giving hydride species and their electrochemical properties are reported.

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Molecular Catalysts for Proton Reduction Based on Non‐noble Metals

Cited by 3 publications

References 230 publications

Manganese Complexes: Hydrogen Generation and Oxidation

Manganese Complexes: Hydrogen Generation and Oxidation

Electrocatalytic Proton Reduction by a Cobalt Complex Containing a Proton‐Responsive Bis(alkylimdazole)methane Ligand: Involvement of a C−H Bond in H₂Formation

Tri‐ and Tetra‐Substituted Derivatives of [Fe₂(CO)₆(μ‐dithiolate)] as Novel Dinuclear Platforms Related to the H‐Cluster of [FeFe]H₂ases

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Molecular Catalysts for Proton Reduction Based on Non‐noble Metals

Cited by 3 publications

References 230 publications

Manganese Complexes: Hydrogen Generation and Oxidation

Manganese Complexes: Hydrogen Generation and Oxidation

Electrocatalytic Proton Reduction by a Cobalt Complex Containing a Proton‐Responsive Bis(alkylimdazole)methane Ligand: Involvement of a C−H Bond in H2Formation

Tri‐ and Tetra‐Substituted Derivatives of [Fe2(CO)6(μ‐dithiolate)] as Novel Dinuclear Platforms Related to the H‐Cluster of [FeFe]H2ases

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Electrocatalytic Proton Reduction by a Cobalt Complex Containing a Proton‐Responsive Bis(alkylimdazole)methane Ligand: Involvement of a C−H Bond in H₂Formation

Tri‐ and Tetra‐Substituted Derivatives of [Fe₂(CO)₆(μ‐dithiolate)] as Novel Dinuclear Platforms Related to the H‐Cluster of [FeFe]H₂ases