Investigation of amino acid containing [FeFe] hydrogenase models concerning pendant base effects

Apfel, Ulf‐Peter; Kowol, Christian R.; Halpin, Yvonne; Kloß, Florian; Kübel, Joachim; Görls, Helmar; Vos, Johannes G.; Keppler, Bernhard K.; Morera, Enrico; Lucente, Gino; Weigand, Wolfgang

doi:10.1016/j.jinorgbio.2009.07.005

Cited by 18 publications

(8 citation statements)

References 46 publications

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“…These two compounds were isolated and characterized by X-ray crystallography and found to be [Ru 2 (CO) 6 (μ-SCH 2 CH(NHCO 2 (C(CH 3 ) 3 ))CH 2 S)] ( 2 ) and [Ru 2 (CO) 5 (μ-SCH 2 CH(NHCO 2 (C(CH 3 ) 3 ))CH 2 S)P( o -tol) 3 ] ( 3 ) (Figures and S2 and S3 and Tables S3–S5). An amido–bis(S) ligand-substituted [FeFe] H-cluster model complex with a structure similar to that of complex 2 was previously reported by Weigand’s group . In separate experiments where 2 and 3 were photoirradiated under direct sunlight irradiation, TOFs comparable to that of 1 were obtained.…”

Section: Resultssupporting

confidence: 68%

High-Rate Hydrogen Generation by Direct Sunlight Irradiation with a Triruthenium Complex

Chen

Peng

et al. 2019

Inorg. Chem.

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Herein we report a biomimetic triruthenium catalyst that, when under direct sunlight irradiation, facilitates high-rate H 2 production from formic acid (FA) dehydrogenation. The system consists of 2 μmol of catalyst and 6 μmol of tri-otolylphosphine in 1 mL of dimethylformamide (DMF) and 4 mL of FA/triethylamine (TEA; 5:2). With 0.4 mM catalyst loaded, a high turnover frequency of 1.15 × 10 6 h −1 was detected when under direct sunlight irradiation. In an experiment with 0.2 mM catalyst loaded, more than 140 L of H 2 (280 L of H 2 + CO 2 ) was produced, and a turnover number of approximately 2.78 × 10 6 was obtained within 5 h without decline in H 2 generation activity, making it suitable for high-rate H 2 production.

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Section: Resultssupporting

confidence: 68%

High-Rate Hydrogen Generation by Direct Sunlight Irradiation with a Triruthenium Complex

Chen

Peng

et al. 2019

Inorg. Chem.

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“…Bioinspired structural organometallic mimics of [Fe–Fe] hydrogenases built around a bridging dithiolate ligand have been extensively explored, providing a rich repertoire of chemical structures. These models serve as an important testing ground to assess the features that impart catalytic prowess to the H‐cluster . While most are soluble in organic solvent, several examples of complexes built on a (μ‐S‐(CH 2 ) 3 ‐S)[Fe 2 (CO) 6 ] scaffold and modified with polar groups to facilitate derivatization and/or attachment have been reported .…”

Section: Introductionmentioning

confidence: 99%

“…These models serve as an important testing ground to assess the features that impart catalytic prowesst ot he H-cluster. [12][13][14][15][16][17][18][19][20][21][22][23][24] While most are soluble in organic solvent, severale xamples of complexes built on a( m-S-(CH 2 ) 3 -S)[Fe 2 (CO) 6 ]s caffold and modified with polarg roups to facilitated erivatization and/ora ttachment have been reported. [12][13][14][15][16] Compared to the hydrogenases, these models show moderate catalytic activity,a nd generally are inefficientc atalysts in photoinduced hydrogen production in part becauset hey degrade during long irradiation, often resultingi nt he loss of the CO ligands.…”

Section: Introductionmentioning

confidence: 99%

“…[12][13][14][15][16][17][18][19][20][21][22][23][24] While most are soluble in organic solvent, severale xamples of complexes built on a( m-S-(CH 2 ) 3 -S)[Fe 2 (CO) 6 ]s caffold and modified with polarg roups to facilitated erivatization and/ora ttachment have been reported. [12][13][14][15][16] Compared to the hydrogenases, these models show moderate catalytic activity,a nd generally are inefficientc atalysts in photoinduced hydrogen production in part becauset hey degrade during long irradiation, often resultingi nt he loss of the CO ligands. [17][18][19][20][21][22][23][24][25] Simple diiron-dithiolate complexes have also been encased within biopolymers or non-biological scaffolds, such as cyclodextrins, surfactants, dendrimers, or metal-organic frameworks (MOFs), showingt hat supramolecular confinement enhancesp hotoinduced hydrogen production.…”

Section: Introductionmentioning

confidence: 99%

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Enhanced Photocatalytic Hydrogen Production by Hybrid Streptavidin‐Diiron Catalysts

Vaughn

Tomlin

Booher

et al. 2020

Chemistry A European J

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Hybrid protein–organometallic catalysts are being explored for selective catalysis of a number of reactions, because they utilize the complementary strengths of proteins and of organometallic complex. Herein, we present an artificial hydrogenase, StrepH2, built by incorporating a biotinylated [Fe–Fe] hydrogenase organometallic mimic within streptavidin. This strategy takes advantage of the remarkable strength and specificity of biotin‐streptavidin recognition, which drives quantitative incorporation of the biotinylated diironhexacarbonyl center into streptavidin, as confirmed by UV/Vis spectroscopy and X‐ray crystallography. FTIR spectra of StrepH2 show characteristic peaks at shift values indicative of interactions between the catalyst and the protein scaffold. StrepH2 catalyzes proton reduction to hydrogen in aqueous media during photo‐ and electrocatalysis. Under photocatalytic conditions, the protein‐embedded catalyst shows enhanced efficiency and prolonged activity compared to the isolated catalyst. Transient absorption spectroscopy data suggest a mechanism for the observed increase in activity underpinned by an observed longer lifetime for the catalytic species FeIFe0 when incorporated within streptavidin compared to the biotinylated catalyst in solution.

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“…[26,27] Indeed, there are several experimental results indicating that interactions between the second coordination sphere and surrounding ions and solvent molecules have a pronounced effect on the reactivity of the metal center. [28,29] For instance, the catalytic rate of proton reduction by [Fe 2 (μ-adt H )(CO) 2 (κ 2 -dppv) 2 ] decreases by two orders of magnitude in the presence of a weakly coordinating anion such as BF 4 -, [18] whereas the tautomerization reaction between the N-protonated form and the μ-hydride form of [Fe 2 (μ-adt R )(CO) 4 (PMe 3 ) 2 ] (R = CH 2 C 6 H 5 ) is catalyzed by HCl. [30] Likewise, the reaction of [Fe 2 (μ-pdt)(CO) 4 -(κ 2 -PNP)] {pdt = (SCH 2 ) 2 CH 2 , PNP = (Ph 2 PCH 2 ) 2 NCH 3 } with HBF 4 ·Et 2 O gives a stable N-protonated product in acetone, which further tautomerizes to give a μ-hydride complex in dichloromethane.…”

Section: Introductionmentioning

confidence: 99%

Electrochemical and Computational Study of the Reactivity of a Diiron Azadithiolate Complex towards Protons in the Presence of Coordinating Anions

Bourrez

Gloaguen

2015

Eur J Inorg Chem

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International audienceIn a continued effort to gain understanding of the impact of the second coordination sphere on the catalytic activity of the FeFe-H2ase models, we report the results of an electrochemical and computational study of the reactivity of [Fe2(μ-adtH)(CO)6] {1, adtH = (SCH2)2NH} towards protons in the presence of coordinating anions. The voltammetric behavior of 1 in the presence of HCl (pKa ≈ 9.5) in Bu4NPF6/MeCN is very similar to that of adtR derivatives in the presence of HBF4·Et2O (pKa ≈ 3), suggesting an effect of coordinating anion (i.e. Cl– or BF4–) rather than an effect of acid strength on the catalytic pathway. This hypothesis is supported by DFT calculations, which indicate a weak but significant interaction between Cl– and the proton of the amine group the closest to the metal center in the N-protonated and reduced form of 1

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Investigation of amino acid containing [FeFe] hydrogenase models concerning pendant base effects

Cited by 18 publications

References 46 publications

High-Rate Hydrogen Generation by Direct Sunlight Irradiation with a Triruthenium Complex

High-Rate Hydrogen Generation by Direct Sunlight Irradiation with a Triruthenium Complex

Enhanced Photocatalytic Hydrogen Production by Hybrid Streptavidin‐Diiron Catalysts

Electrochemical and Computational Study of the Reactivity of a Diiron Azadithiolate Complex towards Protons in the Presence of Coordinating Anions

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