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Mononuclear Zr complexes CpZrCl2{eta5-C 5H4(CH2)nCH=CH2} (n = 1, 2, 3) undergo intermolecular metathesis of the vinyl group catalyzed by a Ru complex to produce dinuclear complexes with bridging ligands, (CpZrCl 2)2 {mu-eta5-eta5-C 5H4(CH2)nC5H 4}. Hydrogenation of the products catalyzed by Pd/C affords complexes with a flexible polymethylene chain that bridges two Cp2ZrCl 2 groups. A dinuclear complex with a bridging bisfluorenyl ligand, (CpZrCl2)2(mu-eta5,eta5-C 13H8CH2CH=CHCH2C13H 8), is also obtained from the metathesis of a mononuclear Zr complex with the allylfluorenyl ligand. X-ray crystallography of (CpZrCl 2)2(mu-eta5,eta5-C 13H8CH2CH=CHCH2C13H 8) revealed the molecular structure with a trans-C=C double bond and the two Zr centers situated at different sides of the bridging bisfluorenyl ligand. Cross metathesis reaction of CpZrCl2{eta5-C 5H4(CH2)2CH=CH2} and ferrocenylmethyl acrylate produces the Zr/Fe dinuclear complex CpZrCl 2{mu-eta5,eta5-C5H 4(CH2)2-CH=CHCOOCH2C 5H4}FeCp. The dinuclear complexes catalyze polymerization of ethylene and propylene in the presence of MAO (methylaluminoxane). The activity of the Zr/Zr dinuclear complexes for ethylene polymerization is higher than that of the mononuclear precursors. The length and flexibility of the bridging group of the biscyclopentadienyl ligand also influence the catalytic activity.

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Reference:
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Organometallic Ru(II)-cymene complexes linked to ferrocene (Fc) via nitrogen heterocycles have been synthesized and studied as cytotoxic agents. These compounds are analogues of Ru(II)-arene piano-stool anticancer complexes such as RAPTA-C. The Ru center was coordinated by pyridine, imidazole, and piperidine with 0-, 1-, or 2-carbon bridges to Fc to give six bimetallic, dinuclear compounds, and the properties of these complexes were compared with their non-Fc-functionalized parent compounds. Crystal structures for five of the compounds, their Ru-cymene parent compounds, and an unusual trinuclear compound were determined. Cyclic voltammetry was used to determine the formal MIII/II potentials of each metal center of the Ru-cymene-Fc complexes, with distinct one-electron waves observed in each case. The Fc-functionalized complexes were found to exhibit good cytotoxicity against HT29 human colon adenocarcinoma cells, whereas the parent compounds were inactive. Similarly, antibacterial activity from the Ru-cymene-Fc compounds was observed against Bacillus subtilis, but not from the unfunctionalized complexes. In both cases, the IC50 values correlated quantitatively with the Fc+/0 reduction potentials. This is consistent with more facile oxidation to give ferrocenium, and subsequent generation of toxic reactive oxygen species, leading to greater cytotoxicity. The antioxidant properties of the complexes were quantified by a 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical scavenging assay. EC50 values indicate that linking of the Ru and Fc centers promotes antioxidant activity.

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Reference:
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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The rapid and accurate determination of specific circulating biomarkers at different molecular levels with non- or minimally invasive methods constitutes a major challenge to improve the breast cancer outcomes and life quality of patients. In this field, electrochemical biosensors have demonstrated to be promising alternatives against more complex conventional strategies to perform fast, accurate and on-site determination of circulating biomarkers at low concentrations in minimally treated body fluids. In this article, after discussing briefly the relevance and current challenges associated with the determination of breast cancer circulating biomarkers, an updated overview of the electrochemical affinity biosensing strategies emerged in the last 5 years for this purpose is provided highlighting the great potentiality of these methodologies. After critically discussing the most interesting features of the electrochemical strategies reported so far for the single or multiplexed determination of such biomarkers with demonstrated applicability in liquid biopsy analysis, existing challenges still to be addressed and future directions in this field will be pointed out.

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Reference:
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Alkylferrocenes are obtained in excellent yields by ionic hydrogenation of ferrocenyl aldehydes and ketones using sodium boranuide and trifluoroacetic acid.

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Reference:
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Herein we describe a simple approach for fabrication of microring electrodes by electroless plating a thin layer of gold on polycarbonate (PC) rods. First, the PC rod was exposed to UV light to generate carboxyl groups on the surface. After amination of the surface carboxyl groups by ethylenediamine, the rod was sequentially immersed in HAuCl4 and NaBH4 solutions to form a layer of gold nanoparticles. These gold nanoparticles then functioned as the catalytically active centers for electroless plating thin gold film on the PC rod surface. Finally, the rod surface was thoroughly covered by an insulating glue and fresh microring surface could be obtained easily by laterally cutting with a knife. The electrochemical behavior of thus prepared microring electrodes were characterized by cyclic voltammetry in hydroxymethylferrocene and H2SO4. The whole fabrication process is simple and economic, which can be carried out in ordinary laboratories. In addition, the results of electrocatalytic oxygen reduction demonstrated that the proposed microelectrode could be used as an alternative electrode materials for electrocatalysis and electroanalysis.

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Reference:
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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New ferrocenylalkylimidazolium salts [Fc(CH2)n(C3H3N2)R]X- were synthesised through the incorporation of green chemistry principles of atom economy and when feasible under solvent-free conditions. The products comprise a series of salts all characterised by the ferrocenyl moiety with variations in the length of the linker alkyl chain (n), the size of the imidazolium alkyl substituent (R) or the electronic nature of the counter-ion (X-). The dependence of the physical and electronic properties of the salts on the three main structural variants was studied. It was found that variation in the steric size of the R group has the most profound influence on the melting points of the ionic liquids. The compounds were fully characterised by IR, 1H and 13C NMR, MS and melting point determinations.

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Reference:
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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A new chiral ferrocene-labelled tyrosine PNA monomer 1 has been synthesised in good yield in both racemic and enantiomerically pure forms. It is suitable for insertion in various positions of PNA oligomers, a possibility that has been preliminarily demonstrated by synthesising the dimer 16. Moreover, in view of possible applications to nucleic acid detection, a preliminary voltammetric investigation on the electrochemical activity of monomer 1 and its synthetic precursors has been carried out in DMF. It appears that, despite the bulkiness of the PNA monomer backbone, its insertion on the ferrocene group only moderately lowers the latter’s diffusion coefficients and peak currents, thus affording voltammetric detection limits in the order of 10-6-10 -7 M.

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Reference:
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Cyclic voltammetry was used to create nonequilibrium populations of different solvation and configurational states of partially oxidized polyvinylferrocene (PVF). Oxidation levels were established by scanning either from a fully reduced state to the desired oxidation level or from a fully oxidized state to the desired level. Coulostatic conditions were then established by opening the external circuit, and subsequent mass and potential changes were followed. The film’s approach to equilibrium involves configurational changes within the polymer and simultaneous and subsequent solvent transfer. At very short times (t a¿¿ 0.2 s) the approach to equilibrium is limited by both solvation and reconfiguration processes. For a short time afterward (0.2 < t/s < 1.0) reconfiguration alone is rate limiting. At intermediate times (1 < t/s < 5) both processes play comparable roles. At long times (r > 5 s) solvation is the controlling step. The electroactive polymer film does not completely reach equilibrium even after 1 h at open circuit as evidenced by continuous small mass changes. These mass changes are the result of water transfer between the polymer film and the bathing electrolyte. A scheme of cubes model rationalizes mechanistic pathways leading to equilibrium. In particular, the observed extrema in mass (solvent population) are predicted. The electrode potential, after 1 h at open circuit, shows nearly Nernstian dependence on the redox composition for film states produced by either anodic or cathodic cyclic voltammetric scans. These Nernst plots are displaced by only a few millivolts because only a weak Nernstian dependence on film water content exists. Films that are 50% oxidized exhibit a sub-Nernstian response with respect to the perchlorate concentration in the bathing solution under permselective conditions.

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Reference:
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Vitamin B12 (cobalamin) is the most complex B-type vitamin and is synthetized exclusively in a limited number of prokaryotes. Its biologically active variants contain rare organometallic bonds, which are used by enzymes in a variety of central metabolic pathways such as L-methionine synthesis and ribonucleotide reduction. Although its biosynthesis and role as co-factor are well understood, knowledge about uptake of cobalamin by prokaryotic auxotrophs is scarce. Here, we characterize a cobalamin-specific ECF-type ABC transporter from Lactobacillus delbrueckii, ECF-CbrT, and demonstrate that it mediates the specific, ATP-dependent uptake of cobalamin. We solved the crystal structure of ECF-CbrT in an apo conformation to 3.4 A resolution. Comparison with the ECF transporter for folate (ECF-FolT2) from the same organism, reveals how the identical ECF module adjusts to interact with the different substrate binding proteins FolT2 and CbrT. ECF-CbrT is unrelated to the well-characterized B12 transporter BtuCDF, but their biochemical features indicate functional convergence.

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Reference:
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Superbase-catalyzed (KOH/DMSO suspension as a catalyst) vinylation of hydroxymethyl- and hydroxyethylferrocenes with terminal and internal alkynes (acetylene, propyne, phenylacetylene, 3-ethynylpyridine, 1-propyn-1-yl-benzene, diphenylacetylene) affords hitherto unknown vinyl ethers of ferrocene in 30-93% yields depending on the alkyne structure and the tuneable ratio of reactants/KOH/DMSO. The vinylation smoothly proceeds under mild conditions (70-90 C, 0.25-13 h). With unsubstituted acetylene the process is readily realized under atmospheric pressure (yield of the corresponding vinyl ethers is 81-90%) though under pressure (initial pressure at room temperature is 10-13 atm, maximum pressure is 13-16 atm at the reaction temperature) the yield is close to quantitative (93%). The synthesized compounds were characterized using 1H and 13C NMR, and IR spectroscopy, as well as X-ray diffraction analysis.

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Reference:
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion