[NiFe] Hydrogenases

Dawson, Joe; Perotto, Carlo U.; McMaster, Jonathan; Schröder, Martin

doi:10.1002/9783527664160.ch3

Cited by 5 publications

(8 citation statements)

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“…Numerous other analogous FeFe complexes with a pendant amine have been also synthesized, and they all display HER activity with a lower overpotential compared to their parent compounds without potential proton relay. As a few other examples (Figure 7), complex [9], 38,39 in which two CO on one Fe site have been substituted by a P−N−P ligand, displays HER activity in the presence of HOAc (acetic acid, pK a MeCN = 22.3) with an overpotential of 0.67 V, a value that is much smaller than that measured with the parent complex [2] without pendant amine (η = 1.06 V). However, only a slightly smaller overpotential (η = 0.60 V) has been measured with complex [10], in which an additional potential with a pendant amine at the bridge has been added under similar conditions.…”

Section: Strategies For Optimized Proton Transfersmentioning

confidence: 90%

“…Moreover, the part of H 2 currently produced in a sustainable way (about 1%), called “green hydrogen”, is mainly electrogenerated by water splitting based on Pt, a rare and expensive metal . Some chemists are inspired by nature, and in particular by hydrogenase, enzymes that catalyze H 2 production by reducing protons in a reversible manner, to design molecular electrocatalysts. − In such a context, they focused their efforts not only on mimicking the organometallic complexes responsible for the reactivity present in the active site of the enzymes but also on understanding the mechanism in order to define the key structural features that ensure their efficiency.…”

Section: Introductionmentioning

confidence: 99%

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Bioinspired Molecular Electrocatalysts for H₂Production: Chemical Strategies

2022

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The environmentally friendly production of H2 is one of the major challenges that society has to face in the next decades, as H2 is considered as a promising energy carrier. By taking inspiration from nature, and especially from the two enzymes [NiFe] and [FeFe] hydrogenases, capable of producing H2 catalytically with high rate, efforts have been focused on mimicking the structural and/or functional properties of their active site, i.e., organometallic NiFe and FeFe complexes, respectively. This perspective gives an update on families of bioinspired FeFe and NiFe (electro)catalysts with the aim of emphasing the features that seem to be critical for optimal perfomances: the presence of a (i) nearby electron reservoir or (ii) potential proton relay or (iii) hydride species with specific structural and electronic properties.

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Section: Strategies For Optimized Proton Transfersmentioning

confidence: 90%

Section: Introductionmentioning

confidence: 99%

Bioinspired Molecular Electrocatalysts for H₂Production: Chemical Strategies

2022

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“…Calculations were implemented in the TURBOMOLE package . Among the tested functionals, BP86, ,, TPSS, and B3LYP overestimated the Ni–Ni distance (Table S1 in the Supporting Information). A good match of DFT vs XRD parameters was obtained by the TPSSH and BP86-D3 functionals.…”

Section: Methodsmentioning

confidence: 99%

“…This motif has become topical because it is observed at the active sites of the [NiFe]- and [FeFe]-hydrogenase (H 2 ase) enzymes (Figure ). There has been great interest in elucidating the detailed behavior of these active sites due to the potential of hydrogenase mimics as hydrogen activation catalysts . In terms of catalytic activity and structural similarity, [FeFe]-H 2 ase active site models are much more advanced than [NiFe]-H 2 ase models.…”

Section: Introductionmentioning

confidence: 99%

Effect of Pyramidalization of the M₂(SR)₂ Center: The Case of (C₅H₅)₂Ni₂(SR)₂

et al. 2016

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The effects of simple thiolates vs chelating dithiolates on M−M bonding, redox potentials, and synthetic outcomes have been probed experimentally and computationally. Nickelocene (Cp 2 Ni) has long been known to react with simple thiols to give diamagnetic Cp 2 Ni 2 (SR) 2 with planar Ni 2 S 2 cores and long Ni---Ni distances. Ethane-and propanedithiol (edtH 2 and pdtH 2 , respectively) instead give di-, tri-, and pentanickel complexes, with nonplanar Ni 2 S 2 cores. The 36e Cp 2 Ni 2 (pdt) (1 pdt ) adopts a symmetrical butterfly Ni 2 S 2 structure. Variable-temperature NMR spectra indicate that 1 pdt possesses a thermally accessible triplet state (ΔG = 2.65(5) kcal/mol) in equilibrium with a diamagnetic ground state. DFT calculations indicate that the singlet−triplet gap is highly sensitive to the nonplanarity of the Ni 2 S 2 core. The calculations further reveal that only the high-spin form of 1 pdt features Ni−Ni bonding, which is unprecedented. Cp 2 Ni 3 (pdt) 2 (2 pdt ), which derives from 1 pdt , crystallized as cis and trans isomers, both with a central Ni(pdt) 2 2− unit that is S,Schelated to two CpNi + centers. Reaction of Cp 2 Ni with 1,2-ethanedithiol (H 2 edt) and 1,2-benzenedithiol (bdtH 2 ) exclusively gave the trinickel species 2 edt and 2 bdt , which are structurally analogous to cis-2 pdt . Solutions of 2 edt are unstable, depositing crystals of Cp 2 Ni 5 (edt) 4 (3 edt ). Cyclic voltammetric studies show that the Ni 2 species oxidize readily to give the mixed-valence cations [1 pdt ] + and [1 edt ] + . Crystallographic and EPR analyses indicate that these cations are delocalized mixed-valence Ni(II)− Ni(III) species. Oxidation of Cp 2 Ni 2 (SEt) 2 , which features a planar Ni 2 S 2 core, afforded a mixed-valence cation, showing the pyramidal Ni 2 S 2 core observed in [1 pdt ] 0/+ and [1 edt ] 0/+ . Although not obtained from the Cp 2 Ni/H 2 edt reaction, the neutral complex 1 edt was obtained by reduction of [1 edt ] + . Variable-temperature NMR measurements and DFT calculations indicate that the triplet is further stabilized in this highly pyramidalized species.

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“…Therefore, compartmental nitrogen-based macrocyclic ligands incorporating thiolate bridges are of great interest and will be further described in detail in this section. [55][56][57][58]…”

Section: Compartmental Nitrogen-based Macrocycles Incorporating Thiol...mentioning

confidence: 99%

Fifty Years of Inorganic Biomimetic Chemistry: From the Complexation of Single Metal Cations to Polynuclear Metal Complexes by Multidentate Thiolate Ligands

2023

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This article covers 50 years of coordination chemistry of transition metal complexes and metal-sulfur aggregates involving thiolate-incorporating ligands by reviewing selected examples. The studies in the coordination chemistry of sulfur-rich ligands have been undoubtedly triggered and fed by the concomitant development of bioinorganic chemistry, particularly of iron-sulfur enzymes. The review is broken down in five sections, which examine complexes of increasing nuclearity, including binuclear complexes based on compartmental macrocyclic ligands. We show also how ligand engineering has allowed the researchers in the field to control the nuclearity of the complexes, which was a particularly difficult task for sulfurbased ligands, as thiolates show a strong tendency to coordinate to more than one metal cation at once.

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[NiFe] Hydrogenases

Cited by 5 publications

References 132 publications

Bioinspired Molecular Electrocatalysts for H₂Production: Chemical Strategies

Bioinspired Molecular Electrocatalysts for H₂Production: Chemical Strategies

Effect of Pyramidalization of the M₂(SR)₂ Center: The Case of (C₅H₅)₂Ni₂(SR)₂

Fifty Years of Inorganic Biomimetic Chemistry: From the Complexation of Single Metal Cations to Polynuclear Metal Complexes by Multidentate Thiolate Ligands

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[NiFe] Hydrogenases

Cited by 5 publications

References 132 publications

Bioinspired Molecular Electrocatalysts for H2Production: Chemical Strategies

Bioinspired Molecular Electrocatalysts for H2Production: Chemical Strategies

Effect of Pyramidalization of the M2(SR)2 Center: The Case of (C5H5)2Ni2(SR)2

Fifty Years of Inorganic Biomimetic Chemistry: From the Complexation of Single Metal Cations to Polynuclear Metal Complexes by Multidentate Thiolate Ligands

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Bioinspired Molecular Electrocatalysts for H₂Production: Chemical Strategies

Bioinspired Molecular Electrocatalysts for H₂Production: Chemical Strategies

Effect of Pyramidalization of the M₂(SR)₂ Center: The Case of (C₅H₅)₂Ni₂(SR)₂