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Synthesis, crystal structures, and electrospray ionisation mass spectrometry investigations of ether- And thioether-substituted ferrocenes

A number of ether- and thioether-substituted ferrocenes (1,1?-bis(1,3-dioxane-2-yl)ferrocene 1, 1,1?-bis(5-methyl-1,3- dioxane-2-yl)ferrocene 2, 1,1?-bis(4-methyl-1,3-dioxane-2-yl)ferrocene 3, 1,1?-bis[(R)-(-)-4-methyl-1,3-dioxane-2-yl]ferrocene 4, 1,1?-bis(4,6-dimethyl-1,3-dioxane-2-yl)ferrocene 5, and 1,1?-bis(1,3-dithiane-2-yl)ferrocene 6) were synthesised by direct condensation of 1,1?-diformylferrocene with the corresponding diols or dithiols. The crystal structures of 1, 5a, 5b, and 6 were determined by X-ray diffraction studies. Electrospray ionisation mass spectrometry was used to investigate the binding behaviour of 1 and 6 toward alkali as well as transition metal cations. The dioxane-containing species 1 showed high affinity toward Li+ and Na+, whereas the dithiane derivative 6 bound, as expected, preferentially to Hg2+. The Royal Society of Chemistry 2003.

Synthesis, crystal structures, and electrospray ionisation mass spectrometry investigations of ether- And thioether-substituted ferrocenes

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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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Electrolyte-Free Dye-Sensitized Solar Cell with High Open Circuit Voltage Using a Bifunctional Ferrocene-Based Cyanovinyl Molecule as Dye and Redox Couple

Functionalization of ferrocenyl moieties with a cyanovinyl system using a unique solid-state synthetic method led to the formation of donor-acceptor type compounds with wide absorption in the visible region. A DSSC study using the ferrocenyl cyanovinyl compound as a dye with an electrolyte-free fabrication system showed an unprecedented open-circuit voltage (VOC) of 763-841 mV. DFT calculations were carried out to understand an unique electron transfer mechanism for the DSSC device which may be responsible for the high VOC.

Electrolyte-Free Dye-Sensitized Solar Cell with High Open Circuit Voltage Using a Bifunctional Ferrocene-Based Cyanovinyl Molecule as Dye and Redox Couple

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
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Simple and reliable protocol for metal-free assembling of the bibrachial schiff bases and their reduced derivatives bearing amino acids or short peptide residues

A simple and efficient protocol is developed for the preparation of bibrachial chiral heterodentate ligands bearing two amino acid or peptide side chains on different scaffolds. Copyright

Simple and reliable protocol for metal-free assembling of the bibrachial schiff bases and their reduced derivatives bearing amino acids or short peptide residues

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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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Novel dendrimers containing redox mediator: Enzyme immobilization and applications

In this study, new dendrimers with a ferrocene core were produced by means of a divergent method for the immobilization of the glucose oxidase enzyme (GOx). Pt(II)and Pt(IV)ions were attached to the terminal groups of dendrimers. Metal-containing dendrimers, [Fc(MGlu)2-Aph-Pt(II)]and [Fc(MGlu)2-Aph-Pt(IV)], were obtained using the ?template method? with aminophenol and Pt(II)/Pt(IV)cations. These compounds have been characterized by molar conductivity, magnetic susceptibility, FTIR, UV?Vis, 1H NMR and LC-MS methods. The GOx enzyme was immobilized on the Fc(MGlu)2, [Fc(MGlu)2-Aph-Pt(II)]and [Fc(MGlu)2-Aph-Pt(IV)]dendrimers, and the immobilized enzyme optimization parameters (substrate concentration, temperature, pH, reusability and storage capacity)were determined. Their Km (mM)and Vmax (mM.min?1)values were calculated from the Michaelis?Menten equation. The reusability of the immobilized glucose oxidase enzyme was investigated in an artificial urine medium. The research showed that [Fc(MGlu)2-Aph-Pt(II)]retains more than 61.23% of its initial activity after 10 successive cycles, which is a remarkable result.

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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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Aminomethyl-substituted ferrocenes and derivatives: Straightforward synthetic routes, structural characterization, and electrochemical analysis

A variety of aminomethyl-substituted ferrocenes and the parent compounds (iminomethyl)ferrocenes, azaferrocenophanes, and diferrocenylamines can be selectively synthesized from reductive amination of 1,1?-diformylferrocene or formylferrocene. The optimized one- or two-step reactions have delivered 13 new compounds, isolated in 65-97% yields, which include tertiary (ferrocenylmethyl)amines and azaferrocenophanes by using NaBH(OAc)3 as a mild reducing agent and (iminomethyl)ferrocenes and secondary (ferrocenylmethyl)amines by using LiAlH4. X-ray structures of representative members of these ferrocene derivative families have evidenced the preferred conformation adopted by ferrocene backbones, in which surprisingly the steric hindrance is apparently not systematically minimized. 15N NMR measurements on aminomethyl-substituted ferrocenes and derivatives are provided for the first time, establishing benchmark values ranging from -330 to -305 ppm (nitromethane delta 0 ppm). The cyclic voltammetry of these species evidences two clearly distinct oxidation potentials related to the iron(II) center and the amino function. These aminomethyl-substituted ferrocenes are potentially valuable for further ortho-directed functionalization of ferrocene.

Aminomethyl-substituted ferrocenes and derivatives: Straightforward synthetic routes, structural characterization, and electrochemical analysis

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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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Efficient regio- and diastereo-controlled synthesis of 1,1?- and 1,1?,2,2?-functionalised ferrocenes and the formation of 2-oxa[3]ferrocenophanes

The synthesis of a C2 symmetric 1,1? ,2,2?-tetrasubstituted ferrocene system was discussed. The route involved the reduction of ferrocenyl carbonyl compounds which gave access to a range of alcohols, alkenes, alkanes, ethers, and 2-oxa[3]ferrocenophanes depending on the precise conditions used. The loss of optical activity of 1,1?-bis(hydroxymethyl)ferrocenes and 1,1?-bis(hydroxymethyl)ruthenocenes, which had been prepared by asymmetric reduction, was demonstrated in an acidic medium by extensive 1H NMR studies.

Efficient regio- and diastereo-controlled synthesis of 1,1?- and 1,1?,2,2?-functionalised ferrocenes and the formation of 2-oxa[3]ferrocenophanes

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Ferrocenylpyridines: a new synthesis of 4′-ferrocenylterpyridine and thesingle crystal structure of C3-ferrocenophane, [(eta-C5H4CHCH2C(O)2-C 5H4N)2CHC(O)2-C5H4N]Fe

The synthesis and characterization of the new ligand 4′-ferrocenylterpyridine is reported together with the synthesis and characterization of a new C3-ferrocenophane containing three acetylpyridine units. The terpyridine ligand was prepared in a two-step synthesis from ferrocenecarbaldehyde by aldol condensation and subsequent cyclization. Attempts to prepare the analogous 1,1′-bis-terpyridylferrocene derivative resulted in the formation of a new ferrocenophane: a consequence of inter-annular attackof an anion generated on the side chain of one cyclopentadienyl ring on a carbonyl centre on the side chain of the other cyclopentadienyl ring. The single crystal X-ray structure of this ferrocenophane, [(eta-C5H4 CHCH2C(O)2-C5H4N)2CHC(O)2-C5H4N]Fe, as its dichloromethane solvate, [Fe(C33H27N3O3)].CH2Cl2, has been determined.

Ferrocenylpyridines: a new synthesis of 4′-ferrocenylterpyridine and thesingle crystal structure of C3-ferrocenophane, [(eta-C5H4CHCH2C(O)2-C 5H4N)2CHC(O)2-C5H4N]Fe

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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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Synthesis, characterization and crystal structures of a novel 1,1?-bisferrocenylimine and its monocyclopalladated derivative

The synthesis and characterization of a new 1,1?-bisferrocenylimine [{(eta5-C5H4)-CH{double bond, long}NCy}2Fe] 4 and its monocyclopalladated derivative 6 are reported. The compound 6 was found to be [PdCl{[(eta5-C5H4)-CHO]Fe[(eta 5-C5H3)-CH{double bond, long}NCy]}(PCy3)], which was obtained from the reaction of 4 with two mole equivalents of Li2PdCl4/NaOAc in methanol at room temperature and subsequent treatment of the resulting product with tricyclohexylphosphine (PCy3). The X-ray single-crystal structures of the two new compounds are also described.

Synthesis, characterization and crystal structures of a novel 1,1?-bisferrocenylimine and its monocyclopalladated derivative

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Ferrocenyl-terminated redox stars: Synthesis and electrostatic effects in mixed-valence stabilization

A family of rigid ferrocenyl-terminated redox stars has been synthesizedsby Negishi coupling, including hexa(ferrocenethynyl)benzene complexes, a dodecaferrocenyl star, and stars with extended rigid tetherssand fully characterized. Cyclic voltammetry (CV) studies of the parent complex hexa(ferrocenylethynyl) benzene, 1, show a single wave for the six-electron oxidation of 1 using Nn-Bu4PF6 as the supporting electrolyte on a Pt anode in CH2Cl2, whereas three distinct two-electron reversible CV waves are observed using Nn-Bu 4BArF4 (ArF = 3,5-C 6H3-(CF3)2,). The CV of 1,3,5-tris(ferrocenylethynyl)benzene, 11, also shows only one wave for the three-electron transfer with Nn-Bu4PF6 and three one-electron waves using Nn-Bu4BArF4. This confirms the lack of electronic communication between the ferrocenyl groups and a significant electrostatic effect among the oxidized ferrocenyl groups. This effect is not significant between paraferrocenyl groups in 1,4- bis(ferrocenylethynyl)benzene for which only a single wave is observed even with Nn-Bu4BArF4 as the supporting electrolyte. The para-ferrocenyl substituents are quite independent, which explains that two para-ferrocenyl groups are oxidized at about the same potential in a single CV wave of 1. With the additional steric bulk introduced with a methyl substituent on the ferrocenyl group, however, even the para-methylferrocenyl groups are submitted to a small electrostatic effect splitting the six-electron transfer into six single-electron waves, probably because of the overall steroelectronic constraints. Contrary to 11, 1,3-bis(ferrocenylethynyl)benzene and related complexes with a third, different substituent in the remaining meta position different from a ferrocenylethynyl only show a single two-electron wave using Nn-Bu4BArF4, which is attributed to the transoid conformation of the ferricinium groups minimizing the electrostatic effect. This shows that, in 11, it is the steric frustration that is responsible for the electrostatic effect, and the same occurs in 1. In several cases, DeltaEp is much larger than the expected 60 mV value, characterizing a quasi-reversible (i.e., relatively slow) redox process. It is suggested that this slower electron transfer be attributed to conformational rearrangement of the ferrocenyl groups toward the transoid position in the course of electron transfer. Thus both the thermodynamic and kinetic aspects of the electrostatic factor (isolated from the electronic factor), including the frustration effect, are characterized. The distinction between the electronic communication and through-space electrostatic effect was made possible in all of these complexes in which the absence of wave splitting using a strongly ion-pairing electrolyte shows the absence of significant electronic communication, and was confirmed by the new frustration phenomenon.

Ferrocenyl-terminated redox stars: Synthesis and electrostatic effects in mixed-valence stabilization

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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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Transition metal cation and phosphate anion electrochemical recognition in water by new polyaza ferrocene macrocyclic ligands

New polyaza ferrocene macrocyclic ligands 4-7 have been synthesised and with 4, copper(II) and nickel(II) transition metal complexes isolated. Electrochemical investigations reveal these redox-active ligands can electrochemically sense various transition metal cations in polar organic solvents and in water at high pH values with ligands 4 and 5. Aqueous electrochemical competition experiments with Ni2+, Cu2+ and Zn2+ suggest 4 and 5 exhibit a selectivity preference for the copper(II) cation. At lower pH values (6-8) the respective protonated polyammonium forms of 4, 5 and 7 complex and electrochemically detect the biologically important phosphate anions, ATP and hydrogen phosphate in the aqueous environment.

Transition metal cation and phosphate anion electrochemical recognition in water by new polyaza ferrocene macrocyclic ligands

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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