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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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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 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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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 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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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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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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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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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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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 series of ferrocene-containing mono- and bis-dihydropyrimidines (DHP’s) were prepared by boric acid mediated three-component Biginelli reactions of formyl- and 1,1?-diformylferrocene, 1,3-dioxo-components and urea. A few further transformations including hydrogenolysis of a benzyl 4-ferrocenyl-DHP-5-carboxylate were also performed. Novel cis-fused saturated pyrimido[4,5-d]pyrimidine-2,7(1H,3H)-diones incorporating [3]-ferrocenophane moiety were constructed by means of iron(III)-catalyzed Biginelli-like condensations of 1,1?-diformylferrocene with urea and in situ generated methyl ketone-derived silyl enol ethers. The structures of the new compounds were established by IR and NMR spectroscopy, including HMQC, HMBC and DEPT measurements.

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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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Title full: Synthesis and characterization of 1,1?-bis[(N-methyl-N-phenyl)aminomethyl(ethyl)]ferrocenes. Crystal structures of [Fe{(eta5-C5H4)-C(C6H 5){double bond, long}N-CH2C6H4CH3-4} 2] and 2[Fe{(eta5-C5H4)-CH2N (CH3)-C6H4OCH3-4}2] · 1/4H2O. Direct or catalytic condensation of diacylferrocenes (acyl = formyl, acetyl, and benzoyl) and anilines or benzylamines with titanium tetrachloride as a catalyst resulted in the corresponding diimines 1-3, respectively. Reduction of these imines with sodium borohydride or lithium aluminum hydride/aluminum chloride in THF yielded 1,1?-bis[(N-phenyl)aminomethyl(ethyl)]ferrocenes (4, 5) and 1,1?-bis[(N-benzyl)aminobenzyl]ferrocenes (6), respectively. Reductive methylation of 4-6 with aqueous formaldehyde, cyanoborohydride and acetic acid only afforded 1,1?-bis[(N-methyl-N-phenyl)aminomethyl(ethyl)]ferrocenes (7, 8). 1,1?-Bis[{(N-methyl-N-benzyl)amino}benzyl]ferrocenes (9) were not obtained, probably due to their debenzylation under the acidic conditions. The molecular structures of 3g and 7a were determined by single crystal X-ray 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

 

Extracurricular laboratory:new discovery of Vinylferrocene

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The forces between colloidal probes and several polymer films were measured by atomic force microscopy in the presence of a series of electrolyte solutions. For Nafion films using a negatively charged silica tip, a repulsive force was obtained at different concentrations of NaClO4. A similar result was obtained for an anion exchange membrane with a positively charged probe. Derjaguin-Landau-Verwey-Overbeek (DLVO) theory was employed to calculate the surface potential and hence, the surface charge. The surface charge density (a¿¼0.3I¼C/cm2) was independent of electrolyte concentration. The slope for plot of potential drop vs In[cs] was a¿¼0.020 V. A theoretical treatment based on GCS theory was employed to account for the above results. For a poly(vinylferrocene) (PVF) film, potential-dependent force curves were obtained, which were qualitatively different from that previously reported for an electronically conducting polymer film electrode.

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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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Palladium-catalyzed enantioselective C(sp2)-H activation of ferrocenyl ketones is achieved through utilizing catalytic, inexpensive l-tert-leucine as a chiral transient directing group. The transformation allows rapid access to ferrocene scaffolds simultaneously possessing planar- and stereogenic central chirality, widely applied in the ferrocene-based chiral ligand families.

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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 improved synthesis of diethyl ferrocenylphosphonate using the tBuLi/tBuOK system at low temperature is reported and the structure of [FcPO3Et2]2 ·ZnCl2complex is described. The electrochemical behaviour of FcP(O)(OEt)2, 1,1?-fc[P(O)(OEt) 2]2, FcCH2P(O)(OEt)2, and their corresponding acids were compared. Each of them shows a reversible one-electron transfer reaction. Ferrocenylbisphosphonate is more difficult to oxidize than ferrocenylphosphonate due to the presence of two electron-withdrawing substituents. A methylene spacer between the ferrocenyl unit and the phosphonate group renders the compound easier to oxidize. The acids are easier to oxidize than the esters, and their salts, in which the phosphonate group behave as an electron-donating group, are even easier to oxidize than the ferrocene. The ferrocenylphosphonic acid may be, then, considered as a redox-active pH responsive molecule. Elsevier B.V. All rights reserved.

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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