Synthesis and Electrocatalytic Property of Diiron Hydride Complexes Derived from a Thiolate-Bridged Diiron Complex

Yang, Dawei; Li, Yang; Wang, Baomin; Zhao, Xingdong; Su, Linan; Chen, Si; Tong, P.; Luo, Yi; Qü, Jingping

doi:10.1021/acs.inorgchem.5b01508

Cited by 58 publications

(44 citation statements)

References 48 publications

(29 reference statements)

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“…Protonation of the Fe(II)( μ -H)Fe(III) complex returns the Fe(III)( μ -H)Fe(III) complex and induces evolution of H 2 (0.5 equiv). 246 These bridging hydride ligands, even on reduced diiron cores, can often be so inert they resist protonation even with strong acids. Indeed, the HER reactions described here can be considered to proceed by an outer-sphere mechanism, throughout which the coordination sphere of the catalyst is unchanged.…”

Section: [Fefe]-h2asesmentioning

confidence: 99%

Hydrogenase Enzymes and Their Synthetic Models: The Role of Metal Hydrides

et al. 2016

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Hydrogenase enzymes efficiently process H2 and protons at organometallic FeFe, NiFe, or Fe active sites. Synthetic modeling of the many H2ase states has provided insight into H2ase structure and mechanism, as well as afforded catalysts for the H2 energy vector. Particularly important are hydride-bearing states, with synthetic hydride analogues now known for each hydrogenase class. These hydrides are typically prepared by protonation of low-valent cores. Examples of FeFe and NiFe hydrides derived from H2 have also been prepared. Such chemistry is more developed than mimicry of the redox-inactive monoFe enzyme, although functional models of the latter are now emerging. Advances in physical and theoretical characterization of H2ase enzymes and synthetic models have proven key to the study of hydrides in particular, and will guide modeling efforts toward more robust and active species optimized for practical applications.

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Section: [Fefe]-h2asesmentioning

confidence: 99%

Hydrogenase Enzymes and Their Synthetic Models: The Role of Metal Hydrides

et al. 2016

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“…As shown in Figure 2, the CV curves of complexes 1b – 1f all display a reversible one‐electron reduction event, which is assigned to the Fe II Fe II /Fe II Fe I redox couple. [ 18 ] When all hydrogen atoms in the bdt ligand were substituted by electron‐withdrawing fluoride, the reductive half‐wave potential ( E 1/2 red ) for Fe II Fe II /Fe II Fe I couple of 1b is –0.402 V vs. ferrocene (Fc) +/0 , which is 92 mV more positive than that of 1a . The electron‐donating inductive effect of the tert ‐butyl group in complex 1c is responsible for a significant shift of E 1/2 red toward negative potential ( E 1/2 red = –0.848 V, 354 mV more negative than 1a ).…”

Section: Resultsmentioning

confidence: 99%

Catalytic Disproportionation of Hydrazine Promoted by Biomimetic Diiron Complexes with Benzene‐1,2‐Dithiolate Bridge Modified by Different Substituents

Tie

Yang

et al. 2020

Eur J Inorg Chem

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A series of thiolate‐bridged diiron nitrogenase mimics featuring benzene‐1,2‐dithiolate (bdt) ligand modified by different substituents were synthesized and characterized by X‐ray crystallography. Electrochemical studies by cyclic voltammetry demonstrate the redox potentials of these complexes depend on the electron‐withdrawing or electron‐donating nature of different substituents. Importantly, all these complexes can serve as catalysts for disproportionation of hydrazine to ammonia and dinitrogen, wherein the complex with the most negative reduction potential induced by strong electron‐donating NMe2 group exhibits the best catalytic activity. This result bodes well for efficient catalyst design for N–N bond cleavage of hydrazine. In addition, a well‐defined diiron diazene complex can be independently synthesized and also catalyze the hydrazine disproportionation to ammonia. However, relatively low yield suggests this species may not be a key intermediate during the catalytic cycle, unlike the other reported bimetallic systems.

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“…Related to [ 1 ( μ -H)] + is the symmetrical mixed-valence (Fe II Fe III ) bridging hydride [Cp* 2 Fe 2 (S 2 C 6 H 4 )-( μ -H)] 0 . 44 …”

Section: Resultsmentioning

confidence: 99%

Interplay between Terminal and Bridging Diiron Hydrides in Neutral and Oxidized States

Tung

Wang

et al. 2017

Organometallics

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Graphical Abstract This study describes the structural, spectroscopic, and electrochemical properties of electronically unsymmetrical diiron hydrides. The terminal hydride Cp*Fe(pdt)Fe(dppe)(CO)H ([1(t-H)]0, Cp*− = Me5C5−, pdt2− = CH2(CH2S−)2, dppe = Ph2PC2H4PPh2) was prepared by hydride reduction of [Cp*Fe(pdt)Fe(dppe)(CO)(NCMe)]+. As established by X-ray crystallography, [1(t-H)]0 features a terminal hydride ligand. Unlike previous examples of terminal diiron hydrides, [1(t-H)]0 does not isomerize to the bridging hydride [1(μ-H)]0. Oxidation of [1(t-H)]0 gives [1(t-H)]+, which was also characterized crystallographically as its BF4− salt. Density functional theory (DFT) calculations indicate that [1(t-H)]+ is best described as containing an Cp*FeIII center. In solution, [1(t-H)]+ isomerizes to [1(μ-H)]+, as anticipated by DFT. Reduction of [1(μ-H)]+ by Cp2Co afforded the diferrous bridging hydride [1(μ-H)]0. Electrochemical measurements and DFT calculations indicate that the couples [1(t-H)]+/0 and [1(μ-H)]+/0 differ by 210 mV. Qualitative measurements indicate that [1(t-H)]0 and [1(μ-H)]0 are close in free energy. Protonation of [1(t-H)]0 in MeCN solution affords H2 even with weak acids via hydride transfer. In contrast, protonation of [1(μ-H)]0 yields 0.5 equiv of H2 by a proposed protonation-induced electron transfer process. Isotopic labeling indicates that μ-H/D ligands are inert.

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Synthesis and Electrocatalytic Property of Diiron Hydride Complexes Derived from a Thiolate-Bridged Diiron Complex

Cited by 58 publications

References 48 publications

Hydrogenase Enzymes and Their Synthetic Models: The Role of Metal Hydrides

Hydrogenase Enzymes and Their Synthetic Models: The Role of Metal Hydrides

Catalytic Disproportionation of Hydrazine Promoted by Biomimetic Diiron Complexes with Benzene‐1,2‐Dithiolate Bridge Modified by Different Substituents

Interplay between Terminal and Bridging Diiron Hydrides in Neutral and Oxidized States

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