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The compound bis[1,1?-N,N?-(2-picolyl)aminomethyl]ferrocene, L1, was synthesized. The protonation constants of this ligand and the stability constants of its complexes with Ni2+, Cu2+, Zn2+, Cd2+ and Pb2+ were determined in aqueous solution by potentiometric methods at 25C and at ionic strength 0.10 mol dm-3 in KNO3. The compound L1 forms only 1:1 (M:L) complexes with Pb2+ and Cd2+ while with Ni 2+ and Cu2+ species of 2:1 ratio were also found. The complexing behaviour of L1 is regulated by the constraint imposed by the ferrocene in its backbone, leading to lower values of stability constants for complexes of the divalent first row transition metals when compared with related ligands. However, the differences in stability are smaller for the larger metal ions. The structure of the copper complex with L1 was determined by single-crystal X-ray diffraction and shows that a species of 2:2 ratio is formed. The two copper centres display distorted octahedral geometries and are linked through the two L’ bridges at a long distance of 8.781(10) A. The electrochemical behaviour of L1 was studied in the presence of Ni2+, Cu2+, Zn2+, Cd2+ and Pb2+, showing that upon complexation the ferrocene – ferrocenium half-wave potential shifts anodically in relation to that of the free ligand. The maximum electrochemical shift (DeltaE1/2) of 268 mV was found in the presence of Pb2+ followed by Cu2+ (218 mV), Ni 2+ (152 mV), Zn2- (111 mV) and Cd2+ (110 mV). Moreover, L1 is able to electrochemically and selectively sense Cu2+ in the presence of a large excess of the other transition metal cations studied.

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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 chloro-bridged single-helical chain has been constructed from a ferrocenyl-containing tetranuclear double-helical architecture via self-assembly.

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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 report a fast, mild, efficient and simple Wittig reaction in a dry state to get ferrocenylethene derivatives. The Z and E isomers can be separated by chromatography and many isomers are characterized for the first time.

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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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Respiration, photosynthesis and peroxidase activities of living spherical samples, such as algal protoplasts, breast cancer spheroids and bovine embryos, were characterized with scanning electrochemical microscopy (SECM). The concentration profile of the metabolic product around the spherical sample was directly measured by scanning with a probe microelectrode. According to the spherical diffusion theory, the total mass transfer rate per spherical sample is linear to the multiplication of the sample radius and the concentration difference between the sample surface and the bulk of the solution. Therefore, the sample radius is a key parameter to assess the viability of the living samples. For example, we investigated the respiration and photosynthesis activities as a function of the size of the protoplast (Bryopsis plumosa). The respiration rate was linear to the cube of the sample radius. On the contrary, the photosynthesis rate was linear to the square of the sample radius, suggesting that the former is controlled by the volume of the protoplast, and the latter is controlled by the surface area of the protoplast. We will also discuss the size-dependent activity of the breast cancer spheroids and the bovine embryos. Furthermore, relations between the sample size, the concentration difference, and the oxygen consumption rate of the cryo-preserved bovine blastocysts were investigated.

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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 influence of the reaction conditions in the polycondensation of 1,1′-diacetylferrocene and 1,1′-bisferrocene with biuret is studied and the optimum parameters for obtaining new ferrocene polymers, polyferrocenyleniminoimides, determined.The synthesized polymers are stable up to 225 deg C and show semiconducting properties.

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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 first sumanene-ferrocene probes for efficient and selective caesium cation (Cs+) recognition are reported. The working mechanism of the sumanene moiety as the sensing unit was based on the site-selective cation-pi interaction in its neutral state. The interactions with Cs+ were characterized by high association constant values together with low limits of detection.

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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 In(OTf)3-catalyzed N-benzylation of amines utilizing benzyl alcohols through direct C-O bond activation has been reported. The reaction was performed in water without any base, additive, ligand or inert gas protection to afford the chem-selective mono- or bis-alkylated aromatic amines in good to excellent yields.

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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 discloses a novel containing nitrogen oxygen free radical ferrocene derivatives preparation method and use thereof, of formula (I) is shown containing nitrogen oxygen free radical of the ferrocene derivative or its pharmaceutically acceptable salt or pharmaceutical composition or solvate. (I) in formula (I) indicated by the ferrocene derivative to a lung cancer cell strain A549 and breast cancer cell MCF – 7 of value-added has very strong inhibiting activity, can be used as a medicine for treating cancer, tumor diseases such as candidate compound or a lead compound. (by machine translation)

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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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Synthesis of the (E,E)-1,1?-ferrocene nanostructures having controlled pi-extended conjugation was satisfactory carried out starting of 1?-[2-(1,3-dioxolan)]-1-formylferrocene (1). The molecular unit (E)-1?-[2-(1,3-dioxolan)]-1-[beta-(p-iodophenyl)ethenyl]ferrocene (2), was obtained in excellent yield by treatment of 1 with p-iodobenzyl triphenylphosphonium ylid followed by Z?E isomerization, catalyzed by iodine, in quantitative yield. Compound (E)-2 was transformed in (E)-1?-{2-(1,3-dioxolan)-1-[beta-[4-(3-hydroxy-3-methyl-but-1-ynyl)-phenyl]-ethenyl}ferrocene, (E)-4, by palladium catalyzed cross-coupling with 2-methyl-but-3-yn-2-ol. (E)-4 gives (E)-1-[beta-(4-ethynylphenyl)-ethenyl]-1?-[2-(1,3-dioxolan)]ferrocene (E)-5 by powder sodium hydroxide treatment. The molecular unit (E,E)-1-{beta-[4-(beta-(1?-formylferrocenyl)-ethenyl)-phenylethynyl]-phenyl]-ethenyl}-1?-formylferrocene, (E,E)-6, was synthesized by palladium catalyzed cross-coupling between the p-iodophenyl derivative (E)-2 and their ethynyl derivative (E)-5, in good yield. The (E,E)-1,1?-(p-iodophenyl)ethenyl ferrocene, (E,E)-7, was synthesized by reaction between 1,1?-diformylferrocene and the p-iodobenzyltriphenylphosphonium ylid, as a mixture of isomers which were purely isolated. Moreover, isomerization of the Z,Z and E,Z mixture to the E,E isomer, was induced by sunlight exposure, catalyzed by iodine, in quantitative yield. The (E,E)-1,1?-[beta-(4-ethynylphenyl)-ethenyl]ferrocene, (E,E)-10, was synthesized in good yield, by palladium catalyzed cross-coupling of compound (E,E)-7 with 2-methyl-but-3-yn-2-ol, followed by powder sodium hydroxide treatment.

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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 sustainable and green route to access diverse functionalized ketones via dehydrogenative?dehydrative cross-coupling of primary and secondary alcohols is demonstrated. This borrowing hydrogen approach employing a pincer N-heterocyclic carbene Mn complex displays high activity and selectivity. A variety of primary and secondary alcohols are well tolerant and result in satisfactory isolated yields. Mechanistic studies suggest that this reaction proceeds via a direct outer-sphere mechanism and the dehydrogenation of the secondary alcohol substrates plays a vital role in the rate-limiting step.

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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