HER catalysed by iron complexes without a Fe2S2 core: A review

Agarwal, Tashika; Kaur‐Ghumaan, Sandeep

doi:10.1016/j.ccr.2019.06.019

Cited by 32 publications

(28 citation statements)

References 242 publications

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“…Similar considerations hold true for models 12-15, where the R groups are strongly electron attractors. [72] Since PI has been experimentally observed for some complexes that have a P 2 chelating group, [31,39,40] we extended the study also to models with a chelating -P-R-P-linker, in which the two P atoms are interconnected by a variable length R chain. The investigation of linkers of different length allowed us to evaluate a possible effect of the strain on the value of ΔΔG.…”

Section: Resultsmentioning

confidence: 99%

“…The choice is motivated mainly for two reasons: the resemblance of the Fe 2 L 2 core with the iron clusters found in metalloenzymes which might carry out electron bifurcation, and the large amount of experimental data already available, which allow a critical assessment of the results and conclusions derived from quantum chemical calculations. [31] Although similar to Fe 2 S 2 biomimicry, Fe 2 P 2 complexes show a wellestablished reversible redox behaviour entailing two-electron transfer (excluding very few cases). [32,33] The reversibility of the potential inversion phenomenon makes the Fe 2 P 2 framework particularly interesting in the view of developing a synthetic electron-bifurcating device.…”

Section: Introductionmentioning

confidence: 99%

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Rational Design of Fe₂(μ‐PR₂)₂(L)₆ Coordination Compounds Featuring Tailored Potential Inversion

et al. 2020

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It was recently discovered that some redox proteins can thermodynamically and spatially split two incoming electrons towards different pathways, resulting in the one-electron reduction of two different substrates, featuring reduction potential respectively higher and lower than the parent reductant. This energy conversion process, referred to as electron bifurcation, is relevant not only from a biochemical perspective, but also for the groundbreaking applications that electron-bifurcating molecular devices could have in the field of energy conversion. Natural electron-bifurcating systems contain a two-electron redox centre featuring potential inversion (PI), i. e. with second reduction easier than the first. With the aim of revealing key factors to tailor the span between first and second redox potentials, we performed a systematic density functional study of a 26-molecule set of models with the general formula Fe 2 (μ-PR 2) 2 (L) 6. It turned out that specific features such as i) a FeÀ Fe antibonding character of the LUMO, ii) presence of electrondonor groups and iii) low steric congestion in the Fe's coordination sphere, are key ingredients for PI. In particular, the synergic effects of i)-iii) can lead to a span between first and second redox potentials larger than 700 mV. More generally, the "molecular recipes" herein described are expected to inspire the synthesis of Fe 2 P 2 systems with tailored PI, of primary relevance to the design of electron-bifurcating molecular devices.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Rational Design of Fe₂(μ‐PR₂)₂(L)₆ Coordination Compounds Featuring Tailored Potential Inversion

et al. 2020

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“…[3] The catalysis aided by iron carbonyls has spanned a wide range of areas such as hydrogenation, [4][5][6] hydroxylation, [7] and hydrogen evolution reaction. [8] Iron carbonyls have also been found important roles to play in biology. Two classes of hydrogenase family, [Fe]-and [FeFe]-hydrogenases, employ iron carbonyls as their catalytic active sites which are monoiron carbonyl and diiron carbonyl complexes, respectively.…”

Section: Introductionmentioning

confidence: 99%

“…A large number of iron complexes have been studied in this regard by examining their catalytic property on hydrogen evolution. [2,[8][9][10][11] Iron carbonyl complexes have also drawn one's attention due to the serendipitous discovery of carbon monoxide (CO) in organ transplantation in the 1990s. [12] The discovery unfolded the research of CO in its physiological roles and medical applications.…”

Section: Introductionmentioning

confidence: 99%

Four iron(II) carbonyl complexes containing both pyridyl and halide ligands: Their synthesis, characterization, stability, and anticancer activity

Guo

Jin

Xiao

et al. 2020

Applied Organom Chemis

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Four iron(II) carbonyl complexes, fac-[Fe (CO) 3 X 2 (py)] (X = I − , 1 and Br − , 3), fac-[{Fe (CO) 3 X 2 } 2 (bipy)] (X = I − , 2 and Br − , 4), were facilely synthesized by reacting cis-[Fe (CO) 4 X 2 ] (X = I − , Br −) with pyridine (py) and 4,4 0-dipyridine (bipy) ligands, respectively, in good yields (70%85%). These complexes were fully characterized, and the structures of Complexes 2 and 3 were crystallographically analyzed. In dimethyl sulfoxide, they decomposed rapidly to release carbon monoxide (CO), and in methanol, they showed better stability which allowed kinetically analyzing their decomposing behaviors. The selfdecomposing in methanol fitted first-order kinetics with a half-time ranging from several minutes to 1 h. Our results suggested that the ligand with great conjugation (bipy) and strong electron-donating capability (iodide) could stabilize the iron(II) carbonyl complexes. The decomposition of the iodo complexes (1 and 2) involved the production of iodine radicals. MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromide) assessments revealed that the efficacy against human bladder carcinoma cell line (RT112) is in the following trend: 1 > 2 > 3 > 4. The relatively strong efficacy of Complexes 1 and 2 is mainly contributed to the in situ generated iodine radicals. The combination of the cytotoxicity of the in situ generated radicals with the anticancer activity of CO as reported in literatures may lead to developing novel anticancer drugs with enhanced efficacy. K E Y W O R D S anticancer activity, carbon monoxide release and kinetics, iodine radical, iron carbonyl compounds, solvolysis Zhuming Guo and Jing Jin contributed equally to this work.

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“…Overview of general wisdom on supported catalysts and current knowledge on electrocatalytic HER is summarized in References [41][42][43]. Several fresh reviews deal with more specific catalyst and/or support materials, such as References [44][45][46] for carbon-based supports, References [47,48] for metal-organic frameworks, Reference [49] for 1D and 2D noble metals, and other specific materials in References [50][51][52]. A recent overview of heterostructured HER electrocatalysts can be found in Reference [53].…”

Section: Her At Supported Catalystsmentioning

confidence: 99%

Hydrogen Evolution Reaction-From Single Crystal to Single Atom Catalysts

et al. 2020

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Hydrogen evolution reaction (HER) is one of the most important reactions in electrochemistry. This is not only because it is the simplest way to produce high purity hydrogen and the fact that it is the side reaction in many other technologies. HER actually shaped current electrochemistry because it was in focus of active research for so many years (and it still is). The number of catalysts investigated for HER is immense, and it is not possible to overview them all. In fact, it seems that the complexity of the field overcomes the complexity of HER. The aim of this review is to point out some of the latest developments in HER catalysis, current directions and some of the missing links between a single crystal, nanosized supported catalysts and recently emerging, single-atom catalysts for HER.

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HER catalysed by iron complexes without a Fe2S2 core: A review

Cited by 32 publications

References 242 publications

Rational Design of Fe₂(μ‐PR₂)₂(L)₆ Coordination Compounds Featuring Tailored Potential Inversion

Rational Design of Fe₂(μ‐PR₂)₂(L)₆ Coordination Compounds Featuring Tailored Potential Inversion

Four iron(II) carbonyl complexes containing both pyridyl and halide ligands: Their synthesis, characterization, stability, and anticancer activity

Hydrogen Evolution Reaction-From Single Crystal to Single Atom Catalysts

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HER catalysed by iron complexes without a Fe2S2 core: A review

Cited by 32 publications

References 242 publications

Rational Design of Fe2(μ‐PR2)2(L)6 Coordination Compounds Featuring Tailored Potential Inversion

Rational Design of Fe2(μ‐PR2)2(L)6 Coordination Compounds Featuring Tailored Potential Inversion

Four iron(II) carbonyl complexes containing both pyridyl and halide ligands: Their synthesis, characterization, stability, and anticancer activity

Hydrogen Evolution Reaction-From Single Crystal to Single Atom Catalysts

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Rational Design of Fe₂(μ‐PR₂)₂(L)₆ Coordination Compounds Featuring Tailored Potential Inversion

Rational Design of Fe₂(μ‐PR₂)₂(L)₆ Coordination Compounds Featuring Tailored Potential Inversion