Low-valent Iron Research Articles

From d8 to d1: Iron(0) and Iron(I) Complexes Complete the Series of Eight Fe Oxidation States within the TIMMNMes Ligand Framework.

Reduction of the ferrous precursor [(TIMMNMes)Fe(Cl)]+ (1) (TIMMNMes = tris-[(3-mesitylimidazol-2-ylidene)methyl]amine) to the low-valent iron(0) complex [(TIMMNMes)Fe(CO)3] (2) is presented, where the tris(N-heterocyclic carbene) (NHC) ligand framework remains intact, yet the coordination mode changed from 3-fold to 2-fold coordination of the carbene arms. Further, the corresponding iron(I) complexes [(TIMMNMes)Fe(L)]+ (L = free site, η1-N2, CO, py) (3) are synthesized and fully characterized. Complexes 1-3 demonstrate the notable steric and electronic flexibility of the TIMMNMes ligand framework by variation of the Fe-N anchor and Fe-carbene distances and the variable size of the axial cavity occupation. This is further underpinned by the oxidation of 3-N2 in a reaction with benzophenone to yield the corresponding, charge-separated iron(II) radical complex [(TIMMNMes)Fe(OCPh2)]+ (4). We found rather surprising similarities in the reactivity behavior when going to low- or high-valent oxidation states of the central iron ion. This is demonstrated by the closely related reactivity of 3-N2, where H atom abstraction with TEMPO triggers the formation of the metallacycle [(TIMMNMes*)Fe(py)]+ (5), and the reactivity of the highly unstable Fe(VII) nitride complex [(TIMMNMes)Fe(N)(F)]3+ to give the metallacyclic Fe(V) imido complex [(TIMMNMesN)Fe(NMes)(MeCN)]3+ (6) upon warming. Thus, the employed tris(carbene) chelate is not only capable of stabilizing the superoxidized Fe(VI) and Fe(VII) nitrides but equally supports the iron center in its low oxidation states 0 and +1. Isolation and characterization of these zero- and monovalent iron complexes demonstrate the extraordinary capability of the tris(carbene) chelate TIMMN to support iron in eight different oxidation states within the very same ligand platform.

Cation-Assisted Hydrosilylation of Alkynes Catalyzed by a Low-Valent Iron Complex Bearing Noninnocent Ligands

Cation-Assisted Hydrosilylation of Alkynes Catalyzed by a Low-Valent Iron Complex Bearing Noninnocent Ligands

Adsorption of Glyphosate in Water Using Iron-Based Water Treatment Residuals Derived from Drinking Water Treatment Plants

Glyphosate, a broad-spectrum herbicide, poses a potential threat to human health and the ecosystem due to its toxicity. In this study, iron-based water treatment residuals (Fe-WTRs) were employed for glyphosate removal. The adsorption kinetics, isotherms, and thermodynamics, as well as the effects of pH, Fe-WTR particle size, and temperature, were explored. The results show that Fe-WTRs are an effective adsorbent for glyphosate adsorption, and the maximum uptake capacity was recorded as 30.25 mg/g. The Fe-WTR surface was positively charged, and low-valent iron dominated under acidic conditions, favoring glyphosate adsorption. Furthermore, smaller Fe-WTR particles (<0.125 mm) showed a faster absorption rate and 20% higher adsorption capacity than larger particles (2–5 mm). The kinetic analysis indicated that the adsorption process exhibits a two-step profile, conforming to the pseudo-second-order model, and the thermodynamic analysis indicated that it is a spontaneous, endothermic, and entropy-driven reaction. Finally, the Fourier transform infrared spectral analysis revealed that this process is mainly associated with the formation of metal phosphate through the ligand exchange of the phosphate groups of glyphosates with the hydroxyl groups of iron present in Fe-WTRs. In this study, we demonstrated the potential of Fe-WTRs as a cost-effective and efficient adsorbent for glyphosate removal.

Tuning a phosphine-substituted diimine ligand to afford an iron monocarbonyl complex

A series of low-valent iron complexes that feature a phosphine-substituted α-diimine (DI) ligand have been synthesized. Reduction of (Ph2PPrDI)FeBr2 with an excess of Na/Hg in the presence of carbon monoxide afforded the corresponding dicarbonyl complex, (Ph2PPrDI)Fe(CO)2. Through multinuclear NMR and single crystal X-ray diffraction analysis, this complex was found to possess a 3-coordinate DI ligand. Upon heating for 10 days at 110 °C while applying intermittent vacuum, (Ph2PPrDI)Fe(CO)2 was successfully converted to the corresponding monocarbonyl complex, (Ph2PPrDI)Fe(CO), which was found to feature a tetradentate chelate. Similar reactivity was explored using the analogous bis(tert-butyl)phosphine-substituted ligand, tBu2PPrDI. Addition of this chelate to FeBr2 afforded (tBu2PPrDI)FeBr2, and subsequent reduction yielded (tBu2PPrDI)FeBr, which was found to possess a tridentate DI ligand by single crystal X-ray diffraction. Performing the reduction of (tBu2PPrDI)FeBr2 in the presence of CO afforded the corresponding dicarbonyl complex, (tBu2PPrDI)Fe(CO)2. Like aryl-substituted (Ph2PPrDI)Fe(CO)2, alkyl-substituted (tBu2PPrDI)Fe(CO)2 was found to feature a pendant phosphine arm. However, heating (tBu2PPrDI)Fe(CO)2 under vacuum did not allow for phosphine substitution and conversion to the corresponding monocarbonyl complex, highlighting the importance of phosphine π-acidity for substitution and the stabilization of low-valent iron.

Csp2–H/F bond activation and borylation with low valent iron

Csp2–H/F bond activation and borylation with low valent iron

Chelation-Assisted Iron-Catalyzed C-H Activations: Scope and Mechanism.

ConspectusTo improve the resource economy of molecular syntheses, researchers have developed strategies to directly activate otherwise inert C-H bonds, thus avoiding cumbersome and costly substrate prefunctionalizations. During the past two decades, remarkable progress in coordination chemistry has set the stage for developing increasingly viable metal catalysts for C-H activations. Despite remarkable advances, C-H activations are largely dominated by precious 4d and 5d transition metal catalysts based primarily on palladium, ruthenium, iridium, and rhodium, thus decreasing the inherent sustainable nature of the C-H activation approach. Therefore, advancing catalytic reactions based on Earth-abundant and less toxic 3d transition metals, especially nontoxic and inexpensive iron, represents a desirable and attractive alternative. While research had previously focused on 8-aminoquinoline directing groups in C-H activations, we have devised easily accessible, tunable, and clickable triazoles, which feature widespread applications in bioactive compounds and drugs, among others, as peptide isosteres. Thus, in contrast to other directing groups, the triazole group is a highly desirable structural motif and functions as a bioisostere in medicine and biology, where it is exploited to mimic amide bonds.This Account summarizes the evolution of chelation-assisted iron-catalyzed C-H activations via C-H, C-H/N-H, and C-H/N-H/C-C bond cleavages, with a topical focus on the most recent contributions of our team. Thus, the triazole-enabled iron catalysis has surfaced as a transformative platform for a large variety of C-H transformations, including arylations, alkylations, alkenylations, allylations, annulations, and alkynylations, achieved through C-H activations with organometallic reagents, organohalides, alkynes, alkenes, allenes, and bicyclopropylidenes among others. Consequently, we developed widely applicable methods for the versatile preparation of decorated arenes and heteroarenes, providing access to benzamides, isoquinolones, pyrrolones, pyridones, phenones, indoles, and isoindolinones, among others. Most of these reactions employed 1,2-dichloroisobutane (DCIB) as an oxidant. Notably, chemical-oxidant-free strategies were also developed, with the major breakthroughs being the use of internal oxidants in oxidative annulations, the use of resource-economic electrocatalysis, and the development of well-defined iron(0)-mediated catalysis. In addition, a highly enantioselective inner-sphere C-H alkylation of (aza)indoles was developed by designing novel remotely decorated N-heterocyclic carbene ligands with dispersion energy donors. In addition, detailed mechanistic experiments including kinetic analyses, intermediate isolation, Mößbauer spectroscopy, and computation provided strong support for the mode of catalysis operation, enabling unprecedented C-H activations. Thereby, low-valent iron catalysts paved the way toward weakly coordinating ketones and enantioselective iron-catalyzed C-H activations through organometallic intermediates.

Enhancing ROS-Inducing Nanozyme through Intraparticle Electron Transport.

Iron oxide nanoparticles (IONPs) have garnered significant attention as a promising platform for reactive oxygen species (ROS)-dependent disease treatment, owing to their remarkable biocompatibility and Fenton catalytic activity. However, the low catalytic activity of IONPs is a major hurdle in their clinical translation. To overcome this challenge, IONPs of different compositions are examined for their Fenton reaction under pharmacologically relevant conditions. The results show that wüstite (FeO) nanoparticles exhibit higher catalytic activity than magnetite (Fe3 O4 ) or maghemite (γ-Fe2 O3 ) of matched size and coating, despite having a similar surface oxidation state. Further analyses suggest that the high catalytic activity of wüstite nanoparticles can be attributed to the presence of internal low-valence iron (Fe0 and Fe2+ ), which accelerates the recycling of surface Fe3+ to Fe2+ through intraparticle electron transport. Additionally, ultrasmall wüstite nanoparticles are generated by tuning the thermodecomposition-based nanocrystal synthesis, resulting in a Fenton reaction rate 5.3 times higher than that of ferumoxytol, an FDA-approved IONP. Compared with ferumoxytol, wüstite nanoparticles substantially increase the level of intracellular ROS in mouse mammary carcinoma cells. This study presents a novel mechanism and pivotal improvement for the development of highly efficient ROS-inducing nanozymes, thereby expanding the horizons for their therapeutic applications.

Intramolecular H-Atom Transfers in Alkoxyl Radical Intermediates Underlie the Apparent Oxidation of Lipid Hydroperoxides by Fe(II).

The one-electron reduction of lipid hydroperoxides by low-valent iron species is believed to be a driver of cellular lipid peroxidation and associated ferroptotic cell death. We investigated reactions of cholesterol 7α-OOH, the primary cholesterol autoxidation product, with Fe2+ to find that 7-ketocholesterol (7-KC, an oxidation product) is the major product under these (reducing) conditions. Mechanistic studies reveal the intervention of a 1,2-H-atom shift upon formation of the 7-alkoxyl radical to yield a ketyl radical that can be oxidized by either Fe3+ or O2 to give 7-KC, the most abundant oxysterol in vivo. We also investigated the corresponding reduction of the isomeric cholesterol 5α-OOH and again found that an oxidation product (5-hydroxycholesten-3-one) predominates under reducing conditions. An intramolecular H-atom shift (this time 1,4-) in the initially formed 5-alkoxyl radical is suggested to yield a ketyl radical that is oxidized to give the observed product. It would appear that a 1,2-H shift also accounts for the predominance of ketones over alcohols when unsaturated fatty acid hydroperoxides are exposed to iron-based reductants, which had previously been reported with hematin and demonstrated here with Fe2+. The predominance of 7-KC over the corresponding alcohol is maintained when cholesterol 7α-OOH embedded in phospholipid liposomes is treated with Fe2+ or when ferroptosis is induced in mouse embryonic fibroblasts. Our observation that 7-KC accumulates in ferroptotic cells suggests that it may be a good biomarker for ferroptosis.

Textural properties of ordered nanoporous silica synthesized on mesogenic template

Several synthesis routes have been developed and correlations between the variables of the synthesis procedure and the physicochemical properties of nanoporous silica materials of the MCM-48 type deposited by the template method in the presence of a low-valent iron (II) cation have been investigated. Changes in the structure of silica mesoporous framework, its textural properties and the degree of energy inhomogeneity of the surface were studied depending on the Fe/Si molar ratio, pH values (4 and 9 units), stepwise calcination (673 and 923 K) and extraction of cetylpyridinium template with ethanol from xerogels.

Distribution Characteristics and Genesis of Iron and Manganese Ions in Groundwater of Eastern Sanjiang Plain, China

Groundwater resources are an essential component of global water resources. Long-term consumption of groundwater exceeding the standard levels for iron and manganese can lead to chronic diseases, posing a threat to human health. The Sanjiang Plain is the largest swamp wetland area in China and has high levels of iron and manganese in the groundwater, but the cause still needs to be clarified. Based on the results of water quality tests of 41 groundwater samples in the Eastern Sanjiang Plain, this paper analyzes the distribution characteristics and causes of iron and manganese from the perspectives of the original strata environment, redox conditions, pH conditions, and hydrochemical indicator factors in the research area, using statistical methods and GIS technology. The results show that high iron and manganese content in groundwater is prevalent in the Eastern Sanjiang Plain, and the exceedance rate of manganese is higher than that of iron (87.80% and 82.90%, respectively). The primary sources of iron and manganese in groundwater are iron and manganese minerals in the original strata environment. Influenced by factors such as acidic conditions, reducing environment, and rich organic matter, insoluble high-valent iron and manganese oxides are reduced to low-valent and soluble divalent iron and manganese. At the same time, groundwater’s high mineralization and evaporation concentration are conducive to increased iron and manganese content, while the influence of human activities is small.

Efficient Remediation of p-chloroaniline Contaminated Soil by Activated Persulfate Using Ball Milling Nanosized Zero Valent Iron/Biochar Composite: Performance and Mechanisms.

In this study, efficient remediation of p-chloroaniline (PCA)-contaminated soil by activated persulfate (PS) using nanosized zero-valent iron/biochar (B-nZVI/BC) through the ball milling method was conducted. Under the conditions of 4.8 g kg-1 B-nZVI/BC and 42.0 mmol L-1 PS with pH 7.49, the concentration of PCA in soil was dramatically decreased from 3.64 mg kg-1 to 1.33 mg kg-1, which was much lower than the remediation target value of 1.96 mg kg-1. Further increasing B-nZVI/BC dosage and PS concentration to 14.4 g kg-1 and 126.0 mmol L-1, the concentration of PCA was as low as 0.15 mg kg-1, corresponding to a degradation efficiency of 95.9%. Electron paramagnetic resonance (EPR) signals indicated SO4•-, •OH, and O2•- radicals were generated and accounted for PCA degradation with the effect of low-valence iron and through the electron transfer process of the sp2 hybridized carbon structure of biochar. 1-chlorobutane and glycine were formed and subsequently decomposed into butanol, butyric acid, ethylene glycol, and glycolic acid, and the degradation pathway of PCA in the B-nZVI/BC-PS system was proposed accordingly. The findings provide a significant implication for cost-effective and environmentally friendly remediation of PCA-contaminated soil using a facile ball milling preparation of B-nZVI/BC and PS.

Valorization of terpenols under iron catalysis

CC bond formation directly from biomass-derived oxidized hydrocarbons with carbonucleophile utilizing hydrogen auto-transfer is intriguing because it does not generate waste. We demonstrate the use of oxidized terpenes derived from natural sources such as essential oils for the direct alkylation of oxindoles employing a well-defined earth-abundant low-valent iron complex. The scope of the reaction is extremely broad, and numerous terpenols, including geraniol, nerol, prenol, farnesol, geranylgeraniol, phytol, and solanesol, can be utilized. Furthermore, the developed method can also extend to non-natural synthetic terpenols. A plausible catalytic cycle is proposed based on a series of in-depth mechanistic studies, kinetic experiments, and DFT analyses.

Iron/Photosensitizer-Catalyzed Directed C–H Activation Triggered by the Formation of an Iron Metallacycle

C–H functionalization reactions catalyzed by iron, the most abundant transition metallic element in the Earth’s crust, are one of the ideal synthetic methods. However, there are a limited number of strategies for iron-catalyzed directed C–H activation reactions when compared to reactions catalyzed by other first-row transition metals. Here, we report the iron/photosensitizer-catalyzed C–H alkenylation of amide derivatives via a σ-CAM (σ-complex-assisted metathesis) promoted by the in situ generation of an iron metallacycle. Mechanistic experiments suggest that the C–H bond cleavage would proceed via the σ-CAM from a metallacycle generated in situ rather than via the oxidative addition to a low-valent iron species.

Structural modulation of low-valent iron in LDH-derived Ni3Se4nanosheets: a breakthrough electrocatalyst for the overall water splitting reaction

Here an LDH-derived microporous Fe@Ni3Se4with enriched redox active Fe2+ion is reported. The same has acquired 10 mA cm−2current density with 185 and 33 mV of overpotential value in alkaline condition with high specific activity and durability.

Genetic mechanism of Carboniferous-Permian coal measures siderite nodules in an epicontinental sea basin—An example from the Zibo area in North China

Siderite is a mineral resource and a climate sensitive mineral. Siderite nodule layers are widely developed in coal measures within the marine-ontinental transitional facies of North China epicontinental sea basin, yet their formation environment and genetic mechanism are poorly understood. In this paper, taking the siderite nodule layers in the coal measures of the Late Paleozoic Taiyuan Formation in Zibo area of North China as an example, the formation environment and genetic mechanism of siderite nodules in the transitional facies of the epicontinental sea basin are studied through detailed petrological, sedimentological and geochemical analysis. It is found that the siderite nodules in the research area were formed in a tidal flat-lagoon environment. The siderite nodules are formed in the synsedimentary stage, the original information of chemical composition and characteristics of the nodules being largely retained. Most of the carbon in the siderite nodules originates from inorganic carbon from marine carbonate rocks, with the remainder originating from inorganic carbon formed by dissimilatory iron reducing bacteria (DIR) degrading organic matter. Meanwhile, most of the iron in the siderite nodules originates from hydrothermal fluids, and the remainder from terrigenous sediments. The content of iron input from hydrothermal fluids and terrestrial sediment represents a trade-off relationship. The two genetic mechanisms of the siderite nodules are as follows: 1) Chemical genetic mechanism: The siderite nodules are mainly formed by the combination of low-valence iron (Fe2+) and inorganic carbon in seawater through reduction with iron input from hydrothermal fluids as the main source. 2) Biochemical genetic mechanism: Some is formed by the combination of low-valence iron (Fe2+) and inorganic carbon with high-valence iron (Fe3+) as an oxidant to degrade the organic matter and convert organic carbon into inorganic carbon through DIR. On this basis, a genetic model of the Late Paleozoic coal measures siderite nodules in the epicontinental sea basin is established.

Mechanism of microwave-assisted iron-based catalyst pyrolysis of discarded COVID-19 masks

Inexpensive iron-based catalysts are the most promising catalysts for microwave pyrolysis of waste plastics, especially a large number of disposable medical masks (DMMs) with biological hazards produced by spread of COVID-19. However, most synthesized iron-based catalysts have very low microwave heating efficiency due to the enrichment state of iron. Here, we prepared FeAlOx catalysts using the microwave heating method and found that the microwave heating efficiency of amorphous iron and hematite is very low, indeed, these materials can hardly initiate pyrolysis at room temperature, which limits the application of iron-based catalysts in microwave pyrolysis. By contrast, a mixture of DMMs and low-valent iron oxides produced by hydrogen reduction at 500 °C can be heated by microwaves to temperatures above 900 °C under the same conditions. When the hydrogen reduction temperature was incerased to 800 °C, the content of metallic iron in the catalyst gradually increased from 0.34 to 21.43%, which enhanced the microwave response ability of the catalyst, and decreased the gas content in the pyrolysis product from 78.91 to 70.93 wt%; corresponding hydrogen yield also decreased from 29.03 to 25.02 mmolH2·g-1DMMs. Moreover, the morphology of the deposited solid carbon gradually changed from multi-walled CNTs to bamboo-like CNTs. This study clarifies the pyrolysis mechanism of microwave-assisted iron catalysts and lays a theoretical foundation for their application in microwave pyrolysis.

Iron-Catalyzed Cross-Electrophile Coupling of Inert C–O Bonds with Alkyl Bromides

Iron-Catalyzed Cross-Electrophile Coupling of Inert C–O Bonds with Alkyl Bromides

Forming O–O bonds

<h2>Summary</h2> The ability of transition metal oxides/oxyhydroxides to perform electrocatalytic water splitting is of tremendous interest, particularly for their proclivity to cycle multiple formal oxidation states. The cycling of five oxidation states is central to the oxygen evolution half-reaction (OER) in the absence of peroxide-based mechanisms. The first-row transition metals are of great interest due to their abundance and low toxicity. Many investigators have proposed attack on a metal-oxo motif by water or hydroxide. An alternative mechanism is MO+MO coupling. Here, a thermodynamic model is presented, which explains the trends in first-row transition metal OER electrocatalysts that can form O–O bonds. Based on these cycles, which are supported by experimental thermodynamic data rather than computations, one can predict that vanadium and chromium alone are poor catalysts; titanium may operate by an oxyl-coupling mechanism under irradiation; low-valent manganese, cobalt, iron, and nickel are not likely candidates for attack-based mechanisms; metallic copper is a good candidate; and high-valent iron species supported by nickel could support oxo-oxo coupling chemistry. This model can quantitatively describe experimental measurements on mixed-metal oxides and provide predictions of competent catalysts moving forward.

Iron‐Catalyzed Alkoxycarbonylation of Alkyl Bromides via a Two‐Electron Transfer Process

Transition metal-catalyzed carbonylative cross-coupling reactions are some of the most widely used methods in organic synthesis. However, despite the obvious advantages of iron as an abundant and low toxicity transition metal catalyst, its practical application in carbonylation reaction remains largely unexplored. Here we report our recent study on Fe-catalyzed alkoxycarbonylation of alkyl halides. Mechanistic studies indicate that the reaction is catalyzed by an in situ generated Fe2- complex. This low-valent iron species activates alkyl bromides via a distinctive two-electron transfer (TET) process, whereas it proceeds via a single electron transfer (SET) process for alkyl iodides which is consistent with literature.

Iron-catalyzed decarbonylative borylation enables the one-pot diversification of (Hetero)Aryl and alkyl carboxylic acids

Carboxylic acids are cheap, abundant, and environmentally friendly and are widely employed as partners in cross-coupling reactions. Transition-metal-catalyzed carboxylic acid transformations are typically achieved at extreme temperatures (usually >150°C), significantly limiting their practicality. Here, iron-catalyzed decarbonylation of aryl and alkyl carboxylic acids has been developed, providing the corresponding borylated products with good efficiency. This protocol features excellent functional group compatibility, mild conditions, and the late-stage borylation of bio-relevant carboxylic acids, thus offering excellent opportunities for applications in medicinal chemistry and organic synthesis. Preliminary mechanistic studies suggest that the iron(I)-boryl species may be the crucial intermediate and that a decarbonylative process is involved in this catalytic transformation. • Iron-catalyzed decarbonylative borylation under mild conditions • The generation of low-valent iron species in the iron/borane/alkoxide systems • Iron(I) species may be the crucial intermediate • The involvement of decarbonylative process The transition-metal-catalyzed transformation of carboxylic acids is of great significance. Wen et al. developed an iron-catalyzed decarbonylation of aryl and alkyl carboxylic acids under relatively mild conditions (90°C–130°C), delivering the corresponding borylated products with good efficiency.