Hydrogen Evolution from Aqueous Solutions Mediated by a Heterogenized [NiFe]‐Hydrogenase Model: Low pH Enables Catalysis through an Enzyme‐Relevant Mechanism

Ahmed, Estak; Chattopadhyay, S; Wang, Lianke; Brazzolotto, Deborah; Pramanik, Debajyoti; Aldakov, Dmitry; Fize, Jennifer; Morozan, Adina; Gennari, Marcello; Duboc, Carole; Dey, Abhishek; Artero, Vincent

doi:10.1002/anie.201808215

Cited by 47 publications

(45 citation statements)

References 28 publications

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“…Another milestone was reached when this catalyst was physiadsorbed on a graphite electrode. 54 This followed a first attempt to heterogenize {NiFe′}CO through encapsulation in a MOF that was, however, less promising. 55 The fact that the catalytic performances and mechanism of {NiFe′}CO + and {FeFe′}CO + are comparable suggests that the nature of the metal is not so critical for the reactivity of such hydrogenase mimics.…”

Section: Dihydrogen Production: a Family Of Model Complexes Of Hydrogmentioning

confidence: 99%

Bio-inspired, Multifunctional Metal–Thiolate Motif: From Electron Transfer to Sulfur Reactivity and Small-Molecule Activation

Gennari

Duboc

2020

Acc. Chem. Res.

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Sulfur-rich metalloproteins and metalloenzymes, containing strongly covalent metal-thiolate (cysteinate) or metal-sulfide bonds in their active site, are ubiquitous in nature. The metal-sulfur motif is a highly versatile tool involved in various biological processes: (i) metal storage, transport and detoxification; (ii) electron transfer; (iii) activation of the sulfur atom to promote different types of S-based reactions including S-alkylation, S-oxygenation, S-nitrosylation, disulfide or thiyl radicals formation; (iv) activation of small earth-abundant molecules (such as water, dioxygen, superoxide radical anion, carbon oxides, nitrous oxide and dinitrogen). This Account describes our investigations carried out during the last ten years on bio-inspired and biomimetic low-nuclearity complexes containing metal-thiolate bonds. The general objective of these structural, spectroscopic, electrochemical and catalytic studies was to determine structure-properties-function correlations useful to (i) understand the peculiar features or the mechanism of the mimicked natural systems and/or (ii) reproduce enzymatic reactivities for specific catalytic applications. By employing a unique highly preorganized N2S2-donor ligand with two thiolate functions, in combination with different first-row transition metals (Mn, Fe, Co, Ni, Cu, Zn, V), we got access to a series of bio-inspired sulfur-rich complexes displaying a widespread spectrum of structures, properties and functions. We isolated a dicopper(I) complex that, for the first-time, mimicked concomitantly the key structural, spectroscopic and redox features of the biological CuA center, a highly efficient electron transfer agent involved in the respiratory enzyme cytochrome c oxidase. In the field of sulfur activation, we explored (i) sulfur methylation promoted by a Zn-dithiolate complex that mimics Zn-dependent thiolate alkylation proteins and shows different selectivity compared to the Ni and Co congeners, and (ii) a series of Co, Fe, Mn complexes as the first copper-free systems able to promote thiolate/disulfide interconversion mediated by (de)coordination of halides. Concerning metal-centered reactivity, we investigated two families of metal-thiolate catalysts for small molecule activation, especially relevant in the fields of sustainable fuel production and energy conversion: (i) two isostructural Mn and Fe dinuclear complexes that activate and reduce dioxygen selectively, either to hydrogen peroxide or water as a function of the experimental conditions; (ii) a family of dinuclear MFe (M = Ni, Fe) hydrogenase mimics active for catalytic H2 evolution both in organic solution and on modified electrodes in water. This Account thus illustrates how the versatility of thiolate ligation can support selected functions for transition metal complexes, depending on the nature of the metal, the nuclearity of the complex, the presence and type of co-ligands, the second coordination sphere effects and the experimental conditions.

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Section: Dihydrogen Production: a Family Of Model Complexes Of Hydrogmentioning

confidence: 99%

Bio-inspired, Multifunctional Metal–Thiolate Motif: From Electron Transfer to Sulfur Reactivity and Small-Molecule Activation

Gennari

Duboc

2020

Acc. Chem. Res.

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“…The viability of a hydrogen‐based energy society is depended on efficient and durable production of hydrogen . Recent efforts have resulted in the identification of many molecular catalysts for hydrogen evolution . Despite these achievements, however, understanding and further controlling reaction processes are still highly challenging .…”

Section: Figurementioning

confidence: 99%

Homolytic versus Heterolytic Hydrogen Evolution Reaction Steered by a Steric Effect

Guo

Wang

et al. 2020

Angewandte Chemie

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Several H−H bond forming pathways have been proposed for the hydrogen evolution reaction (HER). Revealing these HER mechanisms is of fundamental importance for the rational design of catalysts and is also extremely challenging. Now, an unparalleled example of switching between homolytic and heterolytic HER mechanisms is reported. Three nickel(II) porphyrins were designed and synthesized with distinct steric effects by introducing bulky amido moieties to ortho‐ or para‐positions of the meso‐phenyl groups. These porphyrins exhibited different catalytic HER behaviors. For these Ni porphyrins, although their 1e‐reduced forms are active to reduce trifluoroacetic acid, the resulting Ni hydrides (depending on the steric effects of porphyrin rings) have different pathways to make H2. Understanding HER processes, especially controllable switching between homolytic and heterolytic H−H bond formation pathways through molecular engineering, is unprecedented in electrocatalysis.

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“…His current interests include multi‐proton and multi‐electron transformations and the development of new analytical techniques to spectroscopically investigate heterogeneous electrocatalysts. Dey was among the authors of a Communication in Angewandte Chemie on hydrogen evolution from aqueous solutions mediated by a heterogenized [NiFe]‐hydrogenase model …”

Section: Awarded …mentioning

confidence: 99%

KNCV Gold Medal: I. K. Voets / SBIC Early Career Award: A. Dey / Malcolm McIntosh Prize: E. J. New / ICS Excellent Young Scientist Prize:C. E. Diesendruck

2019

Angew Chem Int Ed

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Hydrogen Evolution from Aqueous Solutions Mediated by a Heterogenized [NiFe]‐Hydrogenase Model: Low pH Enables Catalysis through an Enzyme‐Relevant Mechanism

Cited by 47 publications

References 28 publications

Bio-inspired, Multifunctional Metal–Thiolate Motif: From Electron Transfer to Sulfur Reactivity and Small-Molecule Activation

Bio-inspired, Multifunctional Metal–Thiolate Motif: From Electron Transfer to Sulfur Reactivity and Small-Molecule Activation

Homolytic versus Heterolytic Hydrogen Evolution Reaction Steered by a Steric Effect

KNCV Gold Medal: I. K. Voets / SBIC Early Career Award: A. Dey / Malcolm McIntosh Prize: E. J. New / ICS Excellent Young Scientist Prize:C. E. Diesendruck

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