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Diamond ultramicroelectrodes

Ultramicroelectrode (UME) tips from conductive diamond were fabricated by hot filament chemical vapour deposition. By changing growth conditions, it was possible to fabricate tips with very smooth nanocrystalline coatings, or relatively rough microcrystalline deposits. Cyclic voltammetry data in ferrocene methanol solution was recorded to characterise the two types of diamond. Nanocrystalline diamond displayed inferior behaviour, both in terms of the potential window, and the background current. Two types of insulation method were studied to complete the microelectrode fabrication process. Nail varnish was found to be easiest to apply and produce the best results. Fast set epoxy produced electrodes with inferior voltammetric characteristics. Electrochemical approach curves were measured under differing conditions for the electrodes studied.

Diamond ultramicroelectrodes

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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-Methyl-4-ferrocenylmethyl-3,5-diphenylpyrazole: A versatile ligand for palladium(II) and platinum(II)

The syntheses and characterization of two novel ferrocene derivatives containing 3,5-diphenylpyrazole units of general formula [1-R-3,5-Ph2-(C3N2)-CH2-Fc] {Fc = (eta5-C5H5)Fe(eta5-C5H4) and R = H (2) or Me (3)} together with a study of their reactivity with palladium(II) and platinum(II) salts or complexes under different experimental conditions is described. These studies have allowed us to isolate and characterize trans-[Pd{1-Me-3,5-Ph2-(C3N2)-CH2-Fc]}2Cl2] (4a) and three different types of heterodimetallic complexes: cis-[M{1-Me-3,5-Ph2-(C3N2)-CH2-Fc]}Cl2(dmso)] {M = Pd (5a) or Pt (5b)}, the cyclometallated products [M{kappa2-C,N-[3-(C6H4)-1-Me-5-Ph-(C3N2)]-CH2-Fc}Cl(L)] with L = PPh3 and M = Pd (6a) or Pt (6b) or L = dmso and M = Pt (8b) and the trans-isomer of [Pt{1-Me-3,5-Ph2-(C3N2)-CH2-Fc]}Cl2(dmso)] (7b). In compounds 4a, 5a, 5b and 7b, the ligand behaves as a neutral N-donor group; while in 6a, 6b and 8b it acts as a bidentate [C(sp2,phenyl),N(pyrazole)]- group. A comparative study of the spectroscopic properties of the compounds, based on NMR, IR and UV-Visible experiments, is also reported.

1-Methyl-4-ferrocenylmethyl-3,5-diphenylpyrazole: A versatile ligand for palladium(II) and platinum(II)

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Reference£º
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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Study of the protection performance of self-assembled monolayers on copper with the scanning electrochemical microscope

The protection performance of self-assembled monolayers (SAMs) formed by 2-(Pyridin-2-yliminomethyl)-phenol (HL) on the surface of copper has been studied in situ with the scanning electrochemical microscope (SECM). The pitting dynamic processes were observed in sodium chloride solution without the presence of SAMs, but they tended to be inhibited by SAMs if the assembly time was long enough. During the scanning process, the self-assembled method decreases the interaction between the HL molecules and the SECM tip greatly.

Study of the protection performance of self-assembled monolayers on copper with the scanning electrochemical microscope

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Reference£º
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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Evaluation of the corrosion performance of coil-coated steel sheet as studied by scanning electrochemical microscopy

This work focuses on the investigation of the very early stages of the degradation of coil-coated galvanized steel sheet through swelling and blistering during exposure to chloride-containing aqueous solutions and the possible effect of the zinc-based metallic coating on the degradation at these very early stages. Three types of coil-coated steel whose difference was in the zinc-based metallic coating, namely galvanized, galfan and aluzinc, were considered. Scanning electrochemical microscopy (SECM) operating in the feedback mode was employed to image topographic changes when the samples were left at their spontaneous open circuit potential. Swelling of the coating and nucleation of blisters were observed for all the samples when they were exposed to naturally aerated 0.1 M KCl solution within 24 h exposure. Conversely, featureless and flat surfaces were found when the samples were either exposed to 0.1 M K2SO4 or to 10 mM KCl. For chloride concentrations of 0.1 M and above the chloride ions were observed to promote coating degradation nearly immediately upon immersion in the electrolyte.

Evaluation of the corrosion performance of coil-coated steel sheet as studied by scanning electrochemical microscopy

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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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Solvent-free reactions of N,N?-thiocarbonyldiimidazole with ferrocenylcarbinols

The efficient and simple routes for the synthesis of various ferrocenyl derivatives from ferrocenylcarbinols and N,N?-thiocarbonyldiimidazole (TCDI) are described. It involves grinding the two substrates in a Pyrex tube with a glass rod at room temperature. The reaction of ferrocenylmethanol (1a) provided S,S-bis(ferrocenylmethyl)dithiocarbonate (1b), whose crystal structure and a plausible mechanism for its formation are also reported. The reaction of 1-ferrocenyl-1-phenylmethanol (2a) and 1-ferrocenylbutanol (2b) gave the products 2c and 2d, respectively. The reaction of omega-ferrocenyl alcohols 4-ferrocenylphenol (3a) and 6-ferrocenylhexan-1-ol (3b) yielded the products 3c and 3d, respectively. Reaction of 1,1?-ferrocenedimethanol (3e) afforded 3f in moderate yield, and by contrast, it was not similar to 1b. Reaction of [4-(trifluoromethyl)phenyl]methanol (4a) provided the thiocarbonate 4b in good yield.

Solvent-free reactions of N,N?-thiocarbonyldiimidazole with ferrocenylcarbinols

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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 thermodynamics of the dissolution of ferrocene and some ferrocenylcarbinols in water

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

The thermodynamics of the dissolution of ferrocene and some ferrocenylcarbinols in water

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Reference£º
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 hexaferrocenyl cluster based on a cyclotriphosphazene core: Synthesis and electrochemistry

Sixfold substitution reaction of hexachlorocyclotriphosphazene with 4-ferrocenylphenol gave a covalent hexaferrocenyl cluster in which all six ferrocene units were electrochemically equivalent. On the other hand, reaction of hexachlorocyclotriphosphazene with ferrocene methanol produced ferrocene aldehyde in high yield.

A hexaferrocenyl cluster based on a cyclotriphosphazene core: Synthesis and electrochemistry

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Reference£º
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 mono and doubly alkynyl substituted ferrocene and its crystal engineering using -C-H¡¤¡¤¡¤O supramolecular synthon

Mono and doubly alkynyl substituted ferrocene complexes, [Fc(CH2OCH2C{triple bond, long}CH)n], 2-3 (2: n = 1; 3: n = 2; Fc = ferrocene) have been synthesized from the room temperature reaction of mono and 1,1?-dihydroxymethyl ferrocene, Fc(CH2OH)n, 1a-b (1a: n = 1; 1b: n = 2) and propargyl bromide, in modest to good yields. These new ferrocene derivatives have been characterized by mass, IR, 1H, 13C NMR spectroscopy, and molecular structures of compound 2 and 3 were unequivocally established by single crystal X-ray diffraction study. The crystal structure analysis revealed that 2 and 3 consist of infinite 1D zig-zag hydrogen bonded chains and 2D microporous hydrogen bonded network of molecules, linked by intermolecular C-H¡¤¡¤¡¤O hydrogen bonding. The molecular structures of both 2 and 3 are further stabilized by C-H¡¤¡¤¡¤pi interactions.

Synthesis of mono and doubly alkynyl substituted ferrocene and its crystal engineering using -C-H¡¤¡¤¡¤O supramolecular synthon

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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 stability of nonporous and macroporous titania thin films in aqueous electrolyte solutions

A simple electrochemical approach was used to evaluate the stability and porosity of titania and silica thin films spin coated on electrode surfaces. This approach involved monitoring the magnitude of the Faradaic current of diffusing redox probes at the modified electrode surfaces over the course of a week to 4.5 months. Relatively nonporous films were examined as well as films templated with polystyrene latex spheres. The results show that templated titania films were significantly more porous compared to non-templated films. After the defect sites in the templated films were blocked, their long-term stability in aqueous electrolyte was evaluated. For titania, blocking was done by spin coating a dilute titania sol on the top of the film whereas for silica, the film was soaked in octyltrimethoxysilane. Both types of titania films (templated and non-templated) were found to be significantly more stable than the corresponding silica films, showing no signs of deterioration in simple electrolyte solutions during the entire evaluation period. In contrast, silica films showed significant deterioration in as little as 3 days. The enhanced stability of the titania films relative to silica films in near neutral electrolyte solutions was attributed to the differences in the point of zero charge of the oxide films.

The stability of nonporous and macroporous titania thin films in aqueous electrolyte solutions

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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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Metallocenes meet porphyrinoids: Consequences of a “fusion”

Historic as well as new developments in chemistry of metallocenyl-containing porphyrins, phthalocyanines, naphthalocyanines, tetraazaporphyrins, subphthalocyanines, subporphyrins, BODIPYs, azaBODIPYs, and related systems were overviewed. Synthetic pathways for preparation as well as the redox and photophysical properties of metallocenyl-type compounds in which organometallic substituents connected to the respective core pi-system via (i) equatorial covalent bond; (ii) axial covalent or coordination bond; (iii) beta,beta’-fusion into the aromatic system; and (iv) eta5- or eta6-bonds to the central metal ion are discussed.

Metallocenes meet porphyrinoids: Consequences of a “fusion”

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Reference£º
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