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We report about a series of mono-nuclear and bi-nuclear complexes with acyclic as well as macro-cyclic ligands, which have been synthesized with Schiff base ligands in tri- tetra and pentadentate forms. The bonding sites on complex formation are mainly the azomethine groups and/or imide nitrogen, ketonic oxygen or sulphur atoms. Complexes of two series of Schiff base ligands, H 2 La and H2 Lb derived from the reaction of 2,6-diacetyl pyridine with semicarbazide, replaced by or thiosemicarbazide with the metal ions, Co(II), Ni(II), Cu(II), VO(IV) and UO2(VI) have been prepared. Mono-nuclear complexes with tetradentate macrocyclic Schiff base ligands, derived from the condensation of 1,1?-diacetylferrocene with 1,3-diaminopropanein in the molar ratio 1:1 and 1:2 have been also synthesized and react with the transition metal ions, copper(II), nickel(II), cobalt(II), and Zinc(II) in the molar ratio 1:1. The structures of these ligands as well as the related complexes are elucidated by different spectroscopic methods. Solvatochromic behavior of copper(II) mixed ligand complexes of 3-acetylcoumarine (3-ACoum) and dinitrogen bases (L), with the general formula Cu(3-ACoum)(L)Xn; where n = 2, L = N,N,-Rfnet-temp?, N?-tetramethylethylenediamine (tmen), 1,10-phenanthroline (phen), 2,2?-bipyridine (bipy) and X = ClO 4-, BF4- or NO3- their synthesis and characterization by elemental analysis, IR, UV-Vis, electron spin resonance spectra, magnetic susceptibility and conductivity measurements is reported. The d-d absorption bands of tmen-complexes in weak donor solvents show the formation of square planar or square pyramidal geometries, whilst the strong donor solvents yield octahedral complexes. The observed solvatochromism is mainly due to the solute-solvent interaction between the chelate cation and the solvent molecules and the spectra displayed the possibility of using these complexes as Lewis base indicators. The Coats-Redfern equation can be used to calculate the kinetic and thermodynamic parameters for the different thermal decomposition steps of some complexes. Cyclic voltagrammes of Co(II) and Ni(II) show quasi-reversible peaks and characterize the redox properties and the nature of the electroactive species of the complexes. Biochemically, both the ligands and the complexes show growth inhibitory activity against pathogenic bacteria and plant pathogenic fungi.

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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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This work describes a method for fabrication of extensive ordered arrays of microelectrodes with varied geometries, surrounded either by an insulating surface of poly(methyl methacrylate) (PMMA) or by a conductive material such as gold or glassy carbon (GC). The method is based on procedures from electron beam lithography (EBL) but, in contrast to classic EBL, it can be applied by using widely available conventional SEM instruments that are not specifically tailored for EBL operation. The electron gun of the SEM is used to irradiate and modify a PMMA film that is covered by a micro- or nano-structured mask (i.e., a TEM grid), which is further selectively revealed. Each array can be evaluated in two configurations, when it is surrounded by the PMMA film, and when it is in contact with the exposed support after PMMA removal. The first configuration is useful to evaluate the electrochemical behavior of pure microelectrode arrays for correlating it with model equations. The second configuration is particularly useful when the substrate material by itself is inactive for the studied reaction. In the latter case, any detected differences between the electrochemical behavior of the PMMA-coated array and that of the bi-component array should come from the contributions of the microelectrode boundaries. These arrays were employed for studying the hydrogen oxidation reaction in alkaline medium on Au/Rh and on GC/Rh in order to detect possible kinetic interactions of both components at the heterojunctions.

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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 hemin/graphene composite, prepared by mixing an aqueous solution of graphene oxide (GO) with hemin and sonicating the suspension for 5 h at room temperature, was investigated for olefination of aldehydes using ethyl diazoacetate in the presence of triphenylphosphine. Efficient olefination of aromatic aldehydes with high (E)-selectivity was obtained, revealing that rGO/hemin is a promising heterogeneous catalyst for the olefination reaction. The as-synthesized catalyst could easily be recovered from the reaction mixture and was subsequently used for several runs without any significantly loss in activity and selectivity.

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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 synthetic procedure based on the aza-Wittig reaction of alpha-azidoacetyl ferrocene or 1,1?-bis(alpha-azidoacetyl)ferrocene with mono-, di-, and triacyl chlorides and triphenylphosphine has been developed to prepare the new homotrimetallic ferrocene complexes 6, 9, and 10 containing at least two oxazole rings in the conjugation chain. Complexes 9 and 10 exhibited three and two reversible redox processes, respectively, indicating significant electrostatic interaction between the iron centers in these complexes. Protonation properties of complexes 9-13 have been assessed by use of 1H NMR and cyclic voltammetry measurements.

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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 enantiomerically pure dibromoferrocene 3 [(Sp,S p)-1,1?-dibromo-2,2?-di(isopropyl)ferrocene], equipped with two iPr groups in alpha positions, was prepared using known “Ugi amine” chemistry. Species 3 was targeted in order to gain access to new [1]ferrocenophanes ([1]FCPs) to be used as monomers for ring-opening polymerization. The iPr groups on the sandwich unit were introduced to stabilize bridging moieties, as well as to increase solubilities of targeted metallopolymers. The planar chiral dibromide 3 can quantitatively be lithiated at 0 C [2 equiv nBuLi, hexanes/thf (9:1), 30 min]. Salt-metathesis reactions with respective element dichloride species gave chiral [1]FCPs with a variety of bridging moieties [ERx=Ga[2-(Me2NCH 2)C6H4] (4 a), SiMe2 (4 b), SntBu2 (4 c), BNiPr2 (4 d)]. The new [1]FCPs were fully characterized including single-crystal X-ray analysis. The stabilizing iPr groups on the Cp rings increase the thermal stabilities of 4 b-d compared to known [1]FCPs, equipped with the same bridging moieties. All three compounds 4 b-d are volatile and could be isolated by vacuum sublimation. Our new approach to [1]FCPs has the potential to overcome many of the existing difficulties in ferrocenophane chemistry, such as limited stability of starting monomers and low solubilities of resulting polyferrocenes. Closing the gap: The preparation of [1]ferrocenophanes with a variety of bridging elements was accomplished by using chiral ferrocene derivatives (see scheme). The isopropyl groups on the sandwich unit serve as protective and solubilizing moieties. The new synthetic approach is superior to the common synthesis of [1]ferrocenophanes, when dilithioferrocene-tmeda is used as the starting material. Copyright

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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 solubilities of ferrocene, ferrocenylcarbinol, methylferrocenylcarbinol, and dimethylferrocenylcarbinol in water at 10-60C are determined. The thermodynamic parameters of the dissolution process are calculated.

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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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1,1?-Diacetylferrocene bis(p-toluenesulfonylhydrazone) and its complex with divalent palladium of composition Pd2LCl2 were synthesized. Infrared, electronic, and 1 H NMR spectroscopy indicate that the semichelate has a cyclopaladinized structure. It is suggested that several forms of the complex exist in solution. Copyright

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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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Gold(i) phosphine complexes are often used in catalysis, but the role of their auxiliary ligands still remains poorly understood. Thus, building on our previous research, we prepared a series of Au(i) complexes [Au2(mu-R2PfcCN)2][SbF6]2 (fc = ferrocene-1,1?-diyl) to assess the effect of phosphine groups PR2 on the catalytic properties of these highly catalytically active, dimeric compounds. Catalytic testing in Au-mediated cyclisation of N-propargyl amides to 2-substituted 5-methyleneoxazolines showed that weaker donating phosphines gave rise to more active, albeit partly destabilised, catalysts. Nevertheless, thanks to their self-stabilisation by reversible nitrile coordination, [Au2(mu-R2PfcCN)2]+ cations readily converted into catalytically active species (by dissociation) and, in addition, remained catalytically active even at very low metal loadings. The experimental results were supported by the trends in 1JPSe coupling constants for R2P(Se)fcCN as a measure of ligand basicity, and by DFT calculations.

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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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Point-of-care testing (POCT) of neurotransmitters, such as dopamine (DA) and 5-hydroxytryptamine (5-HT), can be used for early diagnosis of neurological diseases. Among various POCT platforms, electrochemical method-based platforms have attracted increasing interest owning to their high detection sensitivity and specificity as well as fast response time. In this work, we developed a portable electrochemical POCT platform for detection of neurotransmitters, which is based on integration of a three-dimensional (3D) gold nanoparticles/carbon nanotubes (AuNPs/CNTs) sponge synthesized by a simple in-situ growth and eco-friendly ice-templating method modified screen-printed electrode with a miniaturized USB electrochemical analyzer. We demonstrated the good performance of the portable electrochemical platform for detection of two typical neurotransmitters, i.e., DA and 5-HT, with detection sensitivities of 1.02 muA muM?1 cm?2 and 0.55 muA muM?1 cm?2, and detection limits of 0.06 muM and 0.30 muM for DA and 5-HT, respectively. We further verified the feasibility and practicability of the platform by simultaneous detection of DA and 5-HT in spiked saliva. The developed portable electrochemical platform provides a simple and user-friendly way for early diagnosis of neurological diseases in the future, especially at point of care.

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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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We report an improved synthesis of 1,1?-diaminoferrocene, employing the reduction of 1,1?-diazidoferrocene with H2-Pd/C, along with extensive characterization data for both compounds. Diaminoferrocene undergoes a reversible 1e- oxidation in CH3CN at a potential of -602 mV vs Fc0/+, one of the most negative redox potentials for a ferrocene derivative. The chemical reversibility of this process was confirmed by isolation of the stable, 17-electron [Fc(NH2)2]+ cation as PF6-, OTf-, and TCNE- salts. In the solid state, diaminoferrocene exists in two conformations: one with the NH2 groups eclipsed, and the other with the NH2 groups offset by one-fifth turn around the Cp-Fe-Cp axis. Diazidoferrocene, on the other hand, exhibits only the fully eclipsed conformation in the solid state. The Fe-Cp(centroid) vectors in the diazidoferrocene molecules are roughly aligned with the crystallographic c-axis, and the molecules form layers perpendicular to this axis. The compound is thermally unstable at elevated temperatures, and rapid heating above its melting point results in explosion.

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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