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It has been known since the 1990s that the introduction of a ferrocenyl–type substituent into compounds with proven biological activity can improve their properties. More recently, it was also shown that a carbon bridge connecting the two cyclopentadienyl rings in ferrocene derivatives could enhance the biological properties of the new compounds compared to those without them. However, the synthesis of ferrocenes with this additional linker, known as ansa–ferrocenes, is more difficult due to advanced synthetic protocols and the phenomenon of planar chirality in ring–substituted compounds. As a result, research into the formation of hybrids, conjugates and other ansa–ferrocene derivatives has not been widely conducted. This review discusses the potential biological properties of these units, covering scientific articles published between 1980 and 2024.

The fascinating electrochemical properties of the redox-active compound ferrocene have inspired researchers across the globe to develop ferrocene-based electrocatalysts for a wide variety of applications. Advantages including excellent chemical and thermal stability, solubility in organic solvents, a pair of stable redox states, rapid electron transfer, and nontoxic nature improve its utility in various electrochemical applications. The use of ferrocene-based electrocatalysts enables control over the intrinsic properties and electroactive sites at the surface of the electrode to achieve specific electrochemical activities. Ferrocene and its derivatives can function as a potential redox medium that promotes electron transfer rates, thereby enhancing the reaction kinetics and electrochemical responses of the device. The outstanding electrocatalytic activity of ferrocene-based compounds at lower operating potentials enhances the specificity and sensitivity of reactions and also amplifies the response signals. Owing to their versatile redox chemistry and catalytic activities, ferrocene-based electrocatalysts are widely employed in various energy-related systems, molecular machines, and agricultural, biological, medicinal, and sensing applications. This review highlights the importance of ferrocene-based electrocatalysts, with emphasis on their properties, synthesis strategies for obtaining different ferrocene-based compounds, and their electrochemical applications.

Low-density lipoprotein (LDL) is a cardiac biomarker identified in the pathology of cardiovascular disease (CVD). Typically, the level of LDL is calculated using the Friedewald relationship based on measured values of total cholesterol, high-density lipoproteins (HDL), and triglycerides. Unfortunately, this approach leads to some errors in calculation. Therefore, direct methods that can be used for fast and accurate detection of LDL are needed. The purpose of this study was to develop an electrochemical platform for the detection of LDL based on an antibody–ferrocene conjugate. An anti-apolipoprotein B-100 antibody labeled with ferrocene was covalently immobilized on the layer of 4-aminothiophenol (4-ATP) on the surface of gold electrodes. Upon interaction between LDL and the antibody–ferrocene conjugate, a decrease in the ferrocene redox signal registered by square wave voltammetry was observed, which depends linearly on the concentration from 0.01 ng/mL to 1.0 ng/mL. The obtained limit of detection was equal to 0.53 ng/mL. Moreover, the satisfied selectivity toward human serum albumin (HSA), HDL, and malondialdehyde-modified low-density lipoprotein (MDA-LDL) was observed. In addition, the acceptable recovery rates of LDL in human serum samples indicate the possible application of immunosensors presented in clinical diagnostics.

Ferrocene and its derivatives, especially ferrocene‐based coordination polymers (Fc‐CPs), offer the benefits of high thermal stability, two stable redox states, fast electron transfer, and excellent charge/discharge efficiency, thus holding great promise for electrochemical applications. Herein, we describe the synthesis and electrochemical applications of Fc‐CPs and reveal how the incorporation of ferrocene units into coordination polymers containing other metals results in unprecedented properties. Moreover, we discuss the usage of Fc‐CPs in supercapacitors, batteries, and sensors as well as further applications of these polymers, for example in electrocatalysts, water purification systems, adsorption/storage systems. Iron strength: The incorporation of ferrocene as an organometallic building block into coordination polymers containing other metals to impart certain properties can afford attractive structures denoted as ferrocene‐based coordination polymers. This Review focuses on the synthesis and electrochemical applications (e. g., supercapacitors, batteries, electrosensors, and electrocatalysts) of these coordination polymers.

The synthesis and physical properties of the series of the ferrocenyl-containing sterically hindered phosphonium salts based on di(tert-butyl)ferrocenylphosphine is reported. Analysis of voltamogramms of the obtained compounds revealed some correlations between their structures and electrochemical properties. The elongation of the alkyl chain at the P atom as well as replacement of the Br− anion by [BF4]− shifts the ferrocene/ferrocenium transition of the resulting salts into the positive region. DFT results shows that in the former case, the Br− anion destabilizes the corresponding ion pair, making its oxidation easier due to increased highest occupied molecular orbital (HOMO) energy. Increased HOMO energy for ion pairs with the Br− ion compared to BF4− are caused by contribution of bromide atomic orbitals to the HOMO. The observed correlations can be used for fine-tuning the properties of the salts making them attractive for applications in multicomponent batteries and capacitors.

Ferrocenyl-based compounds have many applications in diverse scientific disciplines, including in polymer chemistry as redox dynamic polymers and dendrimers, in materials science as bioreceptors, and in pharmacology, biochemistry, electrochemistry, and nonlinear optics. Considering the horizon of ferrocene chemistry, we attempted to condense the neoteric advancements in the synthesis and applications of ferrocene derivatives reported in the literature from 2016 to date. This paper presents data on the progression of the synthesis of diverse classes of organic compounds having ferrocene scaffolds and recent developments in applications of ferrocene-based organometallic compounds, with a special focus on their biological, medicinal, bio-sensing, chemosensing, asymmetric catalysis, material, and industrial applications.

Water pollution and scarcity have become major global challenges. The Fenton oxidation method has been widely applied in organic wastewater treatment due to its ability to efficiently degrade toxic organic pollutants. However, traditional homogeneous Fenton systems have several limitations, such as slow reaction rates and the generation of iron sludge. In this study, a ferrocene-based catalytic ultrafiltration membrane was developed by UV photopolymerization. This membrane integrated Fenton reaction with membrane separation technology significantly enhances pollutant removal efficiency, prevents iron sludge formation, and provides self-cleaning properties to extend the service life of the membrane. The results indicated that the ferrocene groups are uniformly distributed on the membrane surface, greatly improving their catalytic efficiency. In heterogeneous Fenton reactions, M2 exhibited excellent catalytic activity, achieving a degradation rate of > 99.9% of methyl orange (MO) within 90 s. Additionally, under the synergistic effect of membrane filtration and catalysis, M2 efficiently removed humic acid (HA) and MO and demonstrated good reusability over multiple cycles. Moreover, under Fenton reaction conditions, M2 showed superior self-cleaning performance, achieving a high FRR value of 94.1%. Overall, this catalytic membrane enhanced pollutant removal efficiency through the combined effect of membrane separation and catalysis, effectively degrading small molecule dyes in the presence of natural organic matter, offering a novel approach to addressing water pollution. [Display omitted] •Ferrocene-functionalized ultrafiltration membrane was prepared using UV photopolymerization.•M2 exhibited high catalytic activity, achieving complete degradation of MO within 90 s.•M2 was able to simultaneously remove both HA and MO from organic wastewater.•M2 demonstrated stability in multiple cyclic operations and outstanding self-cleaning performance.•Mechanistic studies on catalytic reaction indicated that ·O2− and 1O2 played a key role in the degradation reaction.

Two ferrocene derivatives, namely, 1,2-(tetramethylene)-ferrocene and 1,2,1′,2′-bis(tetramethylene)-ferrocene, were synthesized in a four-step reaction sequence starting from ferrocene. Friedel–Crafts acylation of ferrocene using succinic anhydride gave mono- or bis(3-carboxypropinoyl)-ferrocene depending on the stoichiometry of succinic anhydride. The reduction of the keto groups to methylene followed by ring-closing using trifluoroacetic anhydride gave 1,2-(α-ketotetramethylene)-ferrocene or 1,2,1′,2′-bis(α-ketotetramethylene)-ferrocene. The diastereomeric mixture of the latter diketones was separated using column chromatography, characterized via single-crystal X-ray analysis, and assigned its stereochemistry. Reduction of the keto groups to methylene under Clemmensen conditions gave homoannular mono- or bis(tetramethylene)-ferrocene derivatives. The molecular structure of 1,2-(tetramethylene)-ferrocene revealed that the ipso carbon atoms of the cyclopentadienyl group are 0.023(3) Å farther away from Fe(II) compared to the remaining three carbon atoms. Both complexes exhibit lower half-wave oxidation potentials than ferrocene, possibly due to the electron-releasing effects of the tetramethylene bridges.

This manuscript is reviewing the superior catalytic activity and selectivity of ferrocene ligands in a wide range of reactions: reduction of ketones, hydrogenation of olefins, hydroboration, cycloaddition, enantioselective synthesis of biaryls, Tsuji–Trost allylation. Moreover, the correlation between a ligand structure and its catalytic activity is discussed in this review.

The reaction of the diferrocenylphosphenium ion with four terminal allenes follows two different pathways, via allyl or vinyl carbocations, which proceed with electrophilic substitution reactions at one ferrocenyl moiety to form persistent Wheland intermediates and eventually alkenyldiferrocenylphosphonium salts. The reaction of the diferrocenylphosphenium ion with 2‐(trimethylsilyl)‐2,3‐pentadiene affords a stable Wheland intermediate of ferrocene in high yields, which is isolated and fully characterized. A kinetically stable Wheland intermediate of the electrophilic aromatic substitution at ferrocene is isolated from the reaction of the diferrocenylphosphenium ion with the allene 2‐(trimethylsilyl)‐2,3‐pentadiene and fully characterized.