Search results for "tammet"
showing 10 items of 409 documents
A solution study of complex formation between iron(III) and oxalate in dimethylsulphoxide
1991
The complex formation between iron(III) and oxalic acid (ethanedioic acid, H2ox) has been studied by potentiometry in dimethylsulphoxide (dmso) solution. H2ox behaves as a weak diprotic acid in such a solvent, with overall association constants: log βj1=8.551(3) and log βj2=14.242(3) at 25°C and 0.1 Mn-Bu4NClO4. A reliable set of overall stability constants for the iron(III)-oxalato complexes, log β11=13.16(4), log β12=23.66(4) and log β13=30.75(4), have been obtained for the first time under identical conditions. The electrochemical behaviour of such complexes was studied in dmso at a platinum electrode. The coordination ability of oxalate towards iron(III) in dmso and water media is compa…
Unexpected Scholl Reaction of 6,7,13,14-Tetraarylbenzo[k]tetraphene: Selective Formation of Five-Membered Rings in Polycyclic Aromatic Hydrocarbons
2016
Cyclodehydrogenation is a versatile reaction that has enabled the syntheses of numerous polycyclic aromatic hydrocarbons (PAHs). We now describe a unique Scholl reaction of 6,7,13,14-tetraarylbenzo[k]tetraphene, which "unexpectedly" forms five-membered rings accompanying highly selective 1,2-shift of aryl groups. The geometric and optoelectronic nature of the resulting bistetracene analogue with five-membered rings is comprehensively investigated by single-crystal X-ray, NMR, UV-vis absorption, and cyclic voltammetry analyses. Furthermore, a possible mechanism is proposed to account for the selective five-membered-ring formation with the rearrangement of the aryl groups, which can be ration…
Chalcogenide-capped triiron clusters [Fe3(CO)9(μ3-E)2], [Fe3(CO)7(μ3-CO)(μ3-E)(μ-dppm)] and [Fe3(CO)7(μ3-E)2(μ-dppm)] (E = S, Se) as proton-reduction…
2019
Chalcogenide-capped triiron clusters [Fe3(CO)7(μ3-CO)(μ3-E)(μ-dppm)] and [Fe3(CO)7(μ3-E)2(μ-dppm)] (E = S, Se) have been examined as proton-reduction catalysts. Protonation studies show that [Fe3(CO)9(μ3-E)2] are unaffected by strong acids. Mono-capped [Fe3(CO)7(μ3-CO)(μ3-E)(μ-dppm)] react with HBF4.Et2O but changes in IR spectra are attributed to BF3 binding to the face-capping carbonyl, while bicapped [Fe3(CO)7(μ3-E)2(μ-dppm)] are protonated but in a process that is not catalytically important. DFT calculations are presented to support these protonation studies. Cyclic voltammetry shows that [Fe3(CO)9(μ3-Se)2] exhibits two reduction waves, and upon addition of strong acids, proton-reducti…
Novel electrolytes for electrochemical double layer capacitors based on 1,1,1,3,3,3-hexafluoropropan-2-ol
2012
Abstract 1,1,1,3,3,3-Hexafluoropropan-2-ol (HFIP) was tested for its applicability as solvent in electrolytes for energy storage devices. A comprehensive characterization with respect to solubility, conductivity, as well as chemical and electrochemical stability was carried out with different conducting salts. Furthermore, different HFIP solutions containing standard supporting electrolytes and alkali metal fluorides, respectively, were applied in electrochemical double layer capacitor cells. Their behavior was studied with impedance spectroscopy and cyclic voltammetry at low scan rates and compared to the current benchmark electrolytes based on propylene carbonate (PC) and acetonitrile (AN…
The role of lithium, perchlorate and water during electrochemical processes in poly(3,4-ethylenedioxythiophene) films in LiClO4 aqueous solutions
2021
Abstract Thin films of poly(3,4-ethylendioxythiophene) (PEDOT) were electrochemically deposited on gold electrodes in aqueous media. The role of perchlorate, lithium, and water during the charge/discharge of PEDOT films was investigated by cyclic voltammetry together with EQCM, vis − NIR spectroscopy, and acoustic impedance, also by means of ac-electrogravimetry in a 0.1 M LiCl O 4 aqueous solutions. In this way, it has been possible to correlate the electrical, mass, color and electromechanical properties changes during the electrochemical reactions of this polymer. Both, hydrated lithium cations and perchlorate anions can act as counterions during the electrochemical reactions, however, a…
Modelling electrocatalysis of hydroquinone oxidation by nicotinamide adenine dinucleaotide coenzyme encapsulated within SBA-15 and MCM-41 mesoporous …
2006
The electrochemical response of NADH associated to two mesoporous aluminosilicates, MCM-41 and SBA-15, is described upon attachment of such materials into polymer-film electrodes. The studied materials display a significant electrocatalytic activity towards the oxidation of 1,4-dihydrobenzoquinone, H2Q. Two models for describing the electrocatalytic process, based on the general theory of mediated electrocatalysis and the Lovric and Scholz formulation of the voltammetry of microparticles are discussed. Voltammetric and chronoamperometric data indicate that the electrocatalytic process involves the formation of a surface-confined NADH–H2Q adduct in the case of SBA-15, while a surface reactio…
Synthesis, reactivity and structural studies of selenide bridged carboranyl compounds.
2006
Reaction of the lithium salt Li[1-R-1,2-closo-C(2)B(10)H(10)] with selenium under mild conditions, followed by hydrolysis gave the diselenide compound (1-Se-2-R-1,2-closo-C(2)B(10)H(10))(2) in contrast to the well-reported mercapto compounds 1-SH-2-R-1,2-closo-C(2)B(10)H(10) obtained using a similar synthetic procedure. Details for the preparation and X-ray structural characterisation of the new compounds (2-Me-1,2-closo-C(2)B(10)H(10))(2)Se, (1-Se-2-R-1,2-closo-C(2)B(10)H(10))(2) (R = Me, Ph, ) are specified. To further explore the mechanism of the dimerization reaction, the complex [Au(1-Se-2-Me-1,2-closo-C(2)B(10)H(10))(PPh(3))] was synthesized, confirming the existence of the intermedia…
Solid-state electrochemical characterization of emissions and authorities producing Roman brass coins
2020
[EN] The voltammetry of immobilized particles (VIMP) is applied to describe the solid state electrochemistry of brass. This methodology, which involves sampling at the nanogram level, is applied to discriminate mints/authorities producing different Roman monetary emissions covering since the Republic (88 BCE) to Domitianus (55-96 CE) Upon attachment to graphite electrodes in contact with aqueous acetate buffer at pH 4.75, well defined voltarnmetric responses were obtained centered on Cu- and Zn-localized signals whose intensity can be correlated to EMP data, being sensitive to the contents of Zn (15-30 wt.%) and Sn (0.01-1.1 wt.%). Voltammetric data, combined with ATR-FTIR and FIB-PESEM/EDS…
Rare trinuclear NiII2MII complexes (MII = Mn, Fe and Co) with a reduced Schiff base ligand: Synthesis, structures and magnetic properties
2018
Abstract Three new trinuclear hetero-metallic NiII2MII complexes with MII = Mn, Fe and Co have been synthesized using a [NiLR] “metalloligand”, where H2LR = N,N′-bis(2-hydroxybenzyl)-1,3-propanediamine. All complexes have been characterized by elemental analysis, spectroscopic methods, single crystal XRD and magnetic and electrochemical studies. In the three complexes, in addition to the double phenoxido bridges, the two terminal NiII atoms are linked to the central MII [M = Mn(1), Fe(2) and Co(3)] ion by means of a bridging carboxylato co-anion, giving rise to a linear NiII-MII-NiII structure. Variable temperature magnetic susceptibility measurements show the presence of weak ferromagnetic…
Cyclam-functionalized silica-modified electrodes for selective determination of Cu(II)
2009
Cyclam derivatives have been grafted via 1, 2 or 4 silylated arms to the surface of mesoporous silica and the resulting materials have been incorporated into carbon paste electrodes and applied to the preconcentration electroanalysis of Cu(II). Sensitive and selective detection of the target analyte was achieved owing to the attractive binding properties of this macrocyclic ligand towards Cu(II) species. Various parameters likely to affect the preconcentration and detection steps have been studied, including pH of the accumulation medium, composition of the detection solution, structure and composition of the adsorbent, accumulation time, or presence of potentially interfering species. In p…