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Four first- and second-generation heterometallic ferrocenyl derived p-cymene-Ru(II) metallodendrimers, of general formula [DAB-PPI{(kappa6-p-cymene)Ru((C7H5NO)-2-N,O)PTA(5-ferrocenylvinyl)}n][PF6]n and [DAB-PPI{(kappa6-p-cymene)Ru((C6H5N2)-2-N,N)Cl(5-ferrocenylvinyl)}n][PF6]n (where n = 4 (G1), 8 (G2), DAB = 1,4-diaminobutane, PPI = poly(propyleneimine), PTA = 1,3,5-triaza-7-phosphatricyclo[3.3.1.1]decane) have been synthesized. All complexes have been characterized using analytical (i.e., HR-ESI mass spectrometry, HPLC, elemental analysis, and cyclic voltammetry) and spectroscopic (i.e., 1H and 13C{1H} NMR and infrared) methods. Electrochemical studies reveal that the N,O-p-cymene-Ru(II)-PTA complexes result in two irreversible redox processes (oxidation of the Fe(II) and Ru(II) centers), while the N,N-p-cymene-Ru(II) complexes display one reversible wave (Fe(II)/Fe(III) couple). Heterometallic model complexes have been prepared, and for one of the complexes, its molecular structure has been determined by single-crystal X-ray crystallography. In vitro antiproliferation activity of the dendritic ligands and their complexes were evaluated against A2780 and A2780cisR human ovarian cancer lines, the SISO human cervix cancer line, the LCLC-103H human lung cancer line, and the 5637 human bladder cancer line. Nine of the twelve compounds slowed the growth of the ovarian cancer cell lines by more than 50% at equi-iron concentrations of 5 muM.

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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 preparation and twin polymerization of the twin monomer Si(OCH2Fc)4 [Fc = Fe(eta5-C5H4)(eta5-C5H5)] (2) by the reaction of FcCH2OH (1) with SiCl4 in the presence of pyridine was explored. The electronic properties of 2 were investigated by cyclic voltammetry, square-wave voltammetry, and UV/Vis/near-IR spectroelectrochemistry, which showed a redox separation caused by electrostatic repulsion. Thermally induced condensation of 2 is characteristic, as evidenced by differential scanning calorimetry (DSC) and thermogravimetry coupled mass spectrometry (TG-MS). Upon heating 2 to 210 C, twin polymerization occurred and a hybrid material was formed that showed similarities with known systems derived from 2,2?-spirobi[4H-1,3,2-benzodioxasiline] (SBS), such as the nanopatterning of the formed silicon dioxide, which is characteristic for twin polymerization. Electron microscopy of this material revealed the absence of typical microstructuring found for other twin polymers, and hence, the herein presented system can be characterized as a borderline system if compared to known twin monomers such as SBS. The copolymerization of 2 and SBS afforded a hybrid material from which porous carbon or silica materials containing iron oxide nanoparticles could be obtained. The oxidation state of the incorporated particles was examined by Moessbauer experiments, which confirmed that only FeIII was incorporated within the porous carbon and silica materials, respectively. The preparation of iron oxide containing porous carbon capsules was achieved by applying a mixture of 2 and SBS to silicon dioxide spheres (d = 200 nm). After twin polymerization and carbonization, porous carbon capsules with incorporated iron oxide nanostructures were obtained. The straightforward preparation of iron-rich porous carbon and silica materials by twin polymerization of Si(OCH2Fc)4 [Fc = Fe(eta5-C5H4)(eta5-C5H5)] and 2,2?-spirobi[4H-1,3,2-benzodioxasiline] is reported; the electrochemical properties of Si(OCH2Fc)4 are discussed.

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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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Amongst the halogens, the involvement of bromine atoms in various types of intermolecular interactions is comparatively the least studied. In this manuscript, we report the formation of C[sbnd]Br?pi interactions, with the pi-rings being the cyclopentadienyl (Cp) rings of a ferrocene molecule in a newly synthesized compound (E)-1,3-dibromo-5-(2-(ferrocenyl)vinyl)benzene. We have also performed a detailed quantitative analysis on C[sbnd]Br?pi interactions observed in the synthesized molecule and in several related molecules found in the Cambridge Structure Database (CSD) showing the presence of these interactions. A topological analysis based upon QTAIM theory and electrostatic potential ESP mapped on the Hirshfeld surface of these molecules confirm that these interactions are better described as ?halogen bonds? wherein the electropositive region (sigma-hole) on the Br-atom interacts with the electronegative region over the Cp-ring of the ferrocene. Further, the electronegative region on the bromine atom (perpendicular to the C[sbnd]Br bond) was observed to be involved in the formation of highly directional C[sbnd]H?Br interactions with the ?C[sbnd]Br?H close to 90. Thus the bromine atom is acting as both a ?halogen bond donor? and ?hydrogen bond acceptor? in the crystal packing with the two interactions being mutually orthogonal.

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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 ligand, dibenzyl 1,1′-diacetylferrocenebis(hydrazonatocarbodithioate), Fe[C5H4C(CH3)=NNHCSSCH2C6H5)2] (H2Dafhb) and its chelates with lanthanide ions, Ln(Dafhb)Cl (Ln = lanthanide) have been prepared by the reaction of the H2Dafhb with LnCl3. All compounds were characterized by elemental analyses, IR, (1H) NMR, UV, electrolytic conductivity and TGA measurements. It is shown that the ligand coordinates to the metal in the thiol form and that one chloride ion participates in coordination. The chelates are non-electrolytes in DMF and are more thermostable than the ligand due to formation of chelate rings.

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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 surface interrogation mode of scanning electrochemical microscopy (SECM) is extended to the in situ quantification of adsorbed hydrogen, H ads, at polycrystalline platinum. The methodology consists of the production, at an interrogator electrode, of an oxidized species that is able to react with Hads on the Pt surface and report the amounts of this adsorbate through the SECM feedback response. The technique is validated by comparison to the electrochemical underpotential deposition (UPD) of hydrogen on Pt. We include an evaluation of electrochemical mediators for their use as oxidizing reporters for adsorbed species at platinum; a notable finding is the ability of tetramethyl-p-phenylenediamine (TMPD) to oxidize (interrogate) H ads on Pt at low pH (0.5 M H2SO4 or 1 M HClO4) and with minimal background effects. As a case study, the decomposition of formic acid (HCOOH) in acidic media at open circuit on Pt was investigated. Our results suggest that formic acid decomposes at the surface of unbiased Pt through a dehydrogenation route to yield Hads at the Pt surface. The amount of Hads depended on the open circuit potential (OCP) of the Pt electrode at the time of interrogation; at a fixed concentration of HCOOH, a more negative OCP yielded larger amounts of Hads until reaching a coulomb limiting coverage close to 1 UPD monolayer of H ads. The introduction of oxygen into the cell shifted the OCP to more positive potentials and reduced the quantified Hads; furthermore, the system was shown to be chemically reversible, as several interrogations could be run consecutively and reproducibly regardless of the path taken to reach a given OCP.

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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 central challenge of sensor technology is that the sensitivity of analytical detection is required to reach a single analyte entity level, whether it is a molecule, a cell or a nanoparticle. The emergence of nano-impact electrochemistry (NIE) allows in situ detection of single analyte entity one at a time with simplicity, fast response and high throughput. NIE method was originally designed to characterize physical and chemical properties of the corresponding single nanoparticles, and has been later extended into the field of bio-analysis, enabling better understanding of biological heterogeneity and providing new route for developing new diagnostic devices for quantifying biological analytes. A wide range of biological species including DNA, RNA, enzymes, bacteria, vesicles and cells has been already studied using NIE method so far. In this review, we first summarize the basic principles of NIE for bio-analyte detection and then elaborate NIE based bio-analysis categorized by analyte types. Finally, we give an outlook on the future prospects of this field.

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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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In the solid state, molecules of 1,1?-dibenzoylferrocene, [Fe(Cl12H9O)2], (I), are linked to form infinite chains in the [100] direction via (cyclopentadienyl)C – H…O hydrogen bonds [C…O 3.354 (4) A]. In the structure of (4-nitrophenyl)ferrocene, [Fe(C5H5)(C11H8NO2)], (II), there are no C – H-…O hydrogen bonds and molecules are separated by normal van der Waals distances. For earlier determinations see Struchkov [Dokl. Akad. Nauk SSSR (1956), 110, 67-70] for (I) and Roberts et al. [J. Chem. Soc. Dalton Trans. (1988), pp. 1549-1556] for (II).

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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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Technological innovations for the development of self-monitoring systems for health factors are inspirable. Cardiovascular diseases (CVD) have been the major cause in the human mortality rate in recent years. In the present context, development of various cholesterol biosensors as a reliable and self-examining instinct solution for evaluating the biochemical levels in the human body is a contemporary aspiration. In this review, utilization of different polymers, biopolymers and its nanocomposites for biosensor applications have been discussed. Also, factors affecting the performance of cholesterol biosensors are included for a simple and cost-effective biosensors to the global market.

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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 invention comprises a compound characterized by a general formula (1), wherein OM is an organometallic compound independently selected from the group of an unsubstituted or substituted metal sandwich compound, an unsubstituted or substituted half metal sandwich compound or a metal carbonyl compound, and wherein at least one of RL and RR is selected from formula (A), formula (B), formula (C), or formula (D) and their use for in a method of treatment of disease, in particular their use against helminths.

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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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An efficient Rh(III)-catalyzed oxidative olefination by directed C-H bond activation of N-methoxybenzamides is reported. In this mild, practical, selective, and high-yielding process, the N-O bond acts as an internal oxidant. In addition, simply changing the substituent of the directing/oxidizing group results in the selective formation of valuable tetrahydroisoquinolinone products.

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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