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Planar chiral compounds, 1-hydroxymethyl-2-methylferrocene and new 3-(2-hydroxymethylferrocenyl)propanol, were synthesized to be used as dendrimer cores. The ethers of these compounds, namely, 1-(benzyloxymethyl)-2- methylferrocene and 2-(benzyloxymethyl)-1-(benzyloxypropyl)ferrocene, can be regarded as zero-generation Freche type dendrimers. Springer Science+Business Media, Inc. 2006.

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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 construction and characterisation of ring-disk (RD) microelectrodes suitable for use in scanning electrochemical microscopy (SECM) is reported. Such RD electrodes are proposed as probes for novel generator-collector SECM experiments. In this case, the interaction of both the reactants and products with the substrate under investigation can be followed simultaneously from a single approach curve to the substrate. Examples of such approach curves to conducting and insulating substrates are given to demonstrate the potential of this new mode of SECM operation.

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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 crystal structure of tetrakis(cytosine)copper(II) perchlorate dihydrate has been determined. All the hydrogen atoms were obtained from Fourier-difference synthesis. The geometry around copper is a bicapped octahedron (4 + 2 + 2*). The adjacent cytosine rings are oriented head-to-tail with respect to each other and are roughly at right angles to the co-ordination plane. The exocyclic oxo groups form an interligand, intracomplex hydrogen-bonding network above and below the co-ordination plane with the exocyclic amino groups of alternate cytosine bases. The EPR and electronic spectra are consistent with the retention of the solid-state structure in solution. The steric effect of the C(2)=O group of cytosine is offset by the presence of the intracomplex hydrogen-bonding network. The trend in E1/2 values of CuII-CuI couples for 1:4 complexes of cytosine, cytodine, pyridine, 2-methylpyridine and N-methylimidazole suggests that both steric effects and pi-delocalizatiori in imidazole and pyridine ligands and the steric effect of C(2)=O in pyrimidine ligands are important in stabilising CuI relative to CuII.

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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 protocols for controlled reduction of carboxamides to either alcohols or amines were established using a combination of sodium hydride (NaH) and zinc halides (ZnX2). Use of a different halide on ZnX2 dictates the selectivity, wherein the NaH-ZnI2 system delivers alcohols and NaH-ZnCl2 gives amines. Extensive mechanistic studies by experimental and theoretical approaches imply that polymeric zinc hydride (ZnH2)? is responsible for alcohol formation, whereas dimeric zinc chloride hydride (H?Zn?Cl)2 is the key species for the production of amines.

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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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Macro-sized diamond films have been widely applied as the electrode for electrochemical and electroanalytical applications. Due to the non-uniform doping in diamond, boundary effects, and the varied ratios of graphite to diamond, only averaged electrochemical signals are detected over the full electrode. The studies of diamond electrochemistry at the nanoscale are thus highly required. In this chapter we overview recent progress and achievements about electrochemical properties and applications of diamond nanostructures and nanoparticles. After a brief introduction of the formation of these nanostructures and nanoparticles, electrochemical behavior of diamond nanostructures (e.g., diamond nanotexures, nanowires, networks, etc.) and nanoparticles (undoped, doped nanoparticles) in the presence/absence of redox probes is summarized. Their electroanalytical (e.g., electrochemical, biochemical sensing, etc.) and electrochemical (e.g., energy storage using capacitors and batteries, electrocatalysis, etc.) applications are shown. Diamond nanoelectrode array is introduced and highlighted as a promising tool to investigate diamond electrochemistry at the nanoscale as well.

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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 direct process for the trifluoromethylthiolation of allylic and benzylic alcohols under mild conditions has been developed. A wide range of free alcohols underwent nucleophilic substitution in the presence of stable CuSCF3 and BF3·Et2O to give the corresponding products in good to excellent yields.

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The intramolecular M…HO bond in alpha-metallocenylcarbinols (M = Fe, Ru, Os) and the intermolecular Os…HOH bond in the water complex with osmocene have been studied by extended Hueckel (EH) and density functional theory (DFT) methods at the BLYP and B3PW91 levels. There is no evidence that Fe will form such a H-bond. bonds involve the d-orbitals of the more basic Ru and Os atoms, but otherwise appear to be conventional H-bonds. The approximate intramolecular M…H bond energies are 5.0 and 4.1 kcal/mol for Os and Ru, respectively, as compared to 11.7 kcal/mol for the intermolecular Os…HOH bond. The intermolecular M…H-O bond appears to be of linear type with elongation of the H-O distance. There are steric requirements that accompany these H-bonds. The M-ring distances must be long enough in the intramolecular complexes to permit the carbinal to correctly approach the metal; bulky substituents on the cyclopentadienyl rings inhibit intermolecular bonding.

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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 this paper, we have investigated the reactivity of the molybdenum oxide film toward some standard redox systems (e.g., ferrocene (Fc) and its derivatives) and observed a few interesting phenomena. The results demonstrate that the electrochemical behaviour of Fc and its derivatives at the oxide-modified carbon fiber (CF) microelectrode differs from that at a bare CF microelectrode. The conductivity of the molybdenum oxide film is seriously affected by the range and the direction of the potential scan, which influences the electrochemical behaviour of these redox systems at the film electrode. If the cycling potential is more positive than the reduction potential of the molybdenum oxide film, the reduction and oxidation peak currents of Fc and its derivatives could not be observed. The result indicates that the molybdenum oxide film on a microelectrode surface cannot transfer electrons between the surface of the electrode and Fc or its derivatives due to the existence of a high resistance between the interface in these potential ranges. On the other hand, if the lower limit of the scan potential was extended to a potential more negative than the reduction peak potential of the film, the oxidation peak of Fc or its derivatives appeared at about the potential relative to Eo of Fc or its derivatives on the bare electrode, and the peak current is proportional to the concentration of these couples in the electrolyte. To our surprise, the peak height on the modified electrode is much larger than that on the bare CF microelectrode under the same conditions in the range of low concentration of these couples, and the oxidation peak potential of these couples is more negative than that on the bare CF microelectrode. On the basis of the experimental observation, we propose that these redox couples may undergo an interaction with the reduction state of the molybdenum oxide film. The new phenomena that we observed have been explained by using this interaction.

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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 microfabrication and characterization of glass surfaces patterned with enzymes (diaphorase, horseradish peroxidase(HRP)) or antigen-antibodies (carcinoembryonic antigen (CEA), human chorionic gonadotropin (HCG) and human placental lactogen (HPL)) were studied using scanning electrochemical microscopy (SECM). Localized enzymes and antigen-antibody complexes with labeled enzymes were characterized on the basis of detection of catalytic current for ferrocenylmethanol by SECM. The SECM technique was extended to the enzyme-linked immunosorbent assay (ELISA). This method detects as low as ? 104 CEA molecules in a single microspot. We also demonstrated a novel dual assay using microfabricated glass substrates with anti-HCG and anti-HPL microspots.

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

 

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We have synthesized a series of novel SERMs bearing a ferrocenyl unit based on a three-dimensional oxabicyclo[2.2.1]heptene core scaffold. These compounds displayed high receptor binding affinities as well as ERalpha or ERbeta selectivity. In cell proliferation assays, we found that these ligands were cytotoxic at micromolar concentrations in both ER-positive and ER-negative breast cancer cells. On further examination, we found that the antiproliferative effects of compounds 9b, 10h and 11b on MCF-7 cells line does not arise from antiestrogenicity, but rather proceeds through a cytotoxic pathway. Possible mechanisms for the unique activities of these ligands were also investigated by molecular modeling. These new ligands could act as scaffolds for the development of novel anti-breast cancer agents. The Royal Society of Chemistry 2012.

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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