Acetonitrile cyclic voltammetry

Eq. (3), with lithium diisopropylamide (LDA) to a lithiospecies and in its subsequent reaction with C02 affording via the corresponding 4-carboxylic acid its ethyl ester 59. In the alternative version perchlorate 48e is electro-chemically reduced in acetonitrile to an anionic species that was converted either to a 3 1 mixture of isomers 56 (R = f-Bu) and 60 or to 4//-thiopyran 56 (R = PhCH2) with f-BuI or PhCH2Br, respectively (90ACS524). The kinetics of the benzylation procedure was followed by cyclic voltammetry [88ACS(B)269]. 

FIGURE 2-4 Cyclic voltammetry of C60 and C70 in an acetonitrile-toluene solution. (Reproduced with permission from reference 2.)... 

The coordination of redox-active ligands such as 1,2-bis-dithiolates, to the M03Q7 cluster unit, results in oxidation-active complexes in sharp contrast with the electrochemical behavior found for the [Mo3S7Br6] di-anion for which no oxidation process is observed by cyclic voltammetry in acetonitrile within the allowed solvent window [38]. The oxidation potentials are easily accessible and this property can be used to obtain a new family of single-component molecular conductors as will be presented in the next section. Upon reduction, [M03S7 (dithiolate)3] type-11 complexes transform into [Mo3S4(dithiolate)3] type-I dianions, as represented in Eq. (7). 

Fig. 8 Reactions of various carbocations with Kuhn s anion [2 ] as compared with their reduction potentials (peak potentials measured vs. Ag/Ag in acetonitrile by cyclic voltammetry cf. Tables 1 and 8 and Okamoto et al., 1983). SALT, salt formation COV, covalent bond formation ET, single-electron transfer. 

Hoffer S, BaldeUi S, Chou K Ross P, Somorjai GA. 2002. CO oxidation on electrified platinum surfaces in acetonitrile/water solutions studied by sum frequency generation and cyclic voltammetry. J Phys Chem B 106 6473-6478. 

Table 3. Electrochemical data for AT-phenyl-substituted polypyrroles (all data from cyclic voltammetry using 0.1 M Et4NBF4 in acetonitrile exceptab).

Polythiophene films can be electrochemically cycled from the neutral to the conducting state with coulombic efficiencies in excess of 95% [443], with little evidence of decomposition of the material up to + 1.4 V vs. SCE in acetonitrile [37, 54, 56, 396,400] (the 3-methyl derivative being particularly stable [396]), but unlike polypyrrole, polythiophene can be both p- and n-doped, although the n-doped material has a lower maximum conductivity [444], Cyclic voltammetry shows two sets of peaks corresponding to the p- and n-doping reactions, with E° values at approximately + 1.1 V and — 1.4 V respectively (vs. an Ag+/Ag reference electrode)... 

Dynamic properties. On the basis of cyclic voltammetry, Diaz et al. (1981) showed that thin films of polypyrrole on an electrode immersed in acetonitrile could be repeatedly driven between the conducting and insulating states, as shown by the stability of the cyclic voltammograms of the films (see Figure 3.73). 

Polymer films were produced by anodic deposition by potentiostatic deposition onto a platinum electrode. Deposition was done from 1 M solutions of the monomer in 1M LiC104 in acetonitrile. The films were characterized by cyclic voltammetry and reflection infrared spectroscopy in an apparatus described elsewhere [15]. 

The oxidation of hydroxide ion in acetonitrile at copper, silver, gold, and glassy-carbon electrodes has been characterized by cyclic voltammetry. In the absence of bases the metal electrodes are oxidized to their respective cations (Cu+, Ag+, and Au+) at potentials that range from -0.2V vs. SCE for Cu to +1.3 V for Au. At glassy carbon OH is oxidized to 0 - (+0.35 V vs SCE) and then to... 

The redox characteristics, using linear sweep and cyclic voltammetry, of a series of (Z)-6-arylidene-2-phenyl-2,3-dihydrothiazolo[2,3-r][l,2,4]triazol-5(6//)-ones 155 (Figure 24) have been investigated in different dry solvents (acetonitrile, 1,2-dichloroethane, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO)) at platinum and gold electrodes. It was concluded that these compounds lose one electron forming the radical cation, which loses a proton to form the radical. The radical dimerizes to yield the bis-compound which is still electroactive and undergoes further oxidation in one irreversible two-electron process to form the diradical dication on the newly formed C-C bond <2001MI3>. 

FIGURE 1.23. Variations of the transfer coefficient with the electrode potential derived from convolutive cyclic voltammetry of the following systems with double layer correction, t-nitrobutane in acetonitrile ( ), r-nitrobutane in DMF ( ), nitrodurene in acetonitrile + 2%H20 (a), nitrodurene in acetonitrile ( ), nitromesitylene in acetonitrile (y). Data from reference 64 and references therein. 

For the sake of comparison and mutual validation of methods for measuring large follow-up reaction rate constants, it is interesting to apply different methods to the same system. Such a comparison between high-scan-rate ultramicroelectrode cyclic voltammetry, redox catalysis, and laser flash photolysis has been carried out for the system depicted in Scheme 2.25, where methylacridan is oxidized in acetonitrile, generating a cation radical that is deprotonated by a base present in the reaction medium.20... 

Table 1 Anodic peak potentials of common spin traps, determined by cyclic voltammetry in acetonitrile, unless otherwise stated.

Rh(4,4,-(CH3)2bpy)33+/Rh(4,4,-(CH3)2bpy)32+ couple (24). Similarly, E° estimates were obtained from quenching data for other RhL33+ couples (24). In Table 1 these estimates (E°(Q/Q )) are compared with E /2 values obtained via rapid sweep cyclic voltammetry in acetonitrile (Ei/2(CH3CN)). 

MII(bpy )3] is observed (30,31) via cyclic voltammetry in nonaqueous solvents as three 170 mV-separated peaks at -1.2 to -1.3 V vs SCE. The reducibility of the ligand depends on the metal charge and E1/2 for the metal-bound bpy/bpy" couple shifts to less negative potentials as the metal-center charge increases. Thus the first reduction of Ir(bpy)3 +, which occurs at -0.83 V vs SCE in acetonitrile, though 400 mV positive of the MII(bpy)3 +/[MII(bpy)2(bpy )]+ potential, is ascribed to ligand, rather than metal, reduction (41). The... 

Cyclic voltammetry was conducted using a Powerlab ADI Potentiostat interfaced to a computer. A typical three electrode system was used for the analysis Ag/AgCl electrode (2.0 mm) as reference electrode Pt disc (2.0 mm) as working electrode and Pt rod (2.0 mm) as auxiliary electrode. The supporting electrolyte used was a TBAHP/acetonitrile electrolyte-solvent system. The instrument was preset using a Metrohm 693 VA Processor. Potential sweep rate was 200 mV/s using a scan range of-1,800 to 1,800 mV. 

Cyclic voltammetry experiments were controlled using a Powerlab 4/20 interface and PAR model 362 scanning potentiostat with EChem software (v 1.5.2, ADlnstruments) and were carried out using a 1 mm diameter vitreous carbon working electrode, platinum counter electrode, and 2 mm silver wire reference electrode. The potential of the reference electrode was determined using the ferrocenium/ ferrocene (Fc+/Fc) couple, and all potentials are quoted relative to the SCE reference electrode. Against this reference, the Fc /Fc couple occrus at 0.38 V in acetonitrile and 0.53 V in THF [30, 31]. 

The reductive cleavage of iodobenzene and 3-methyliodobenzene was studied by cyclic voltammetry in both DMF and acetonitrile at 21 and 56 °C at different scan rates and has shown that there is a transition between stepwise and concerted mechanisms at lower scan rates. 1-Iodonaphthalene undergoes a stepwise reductive cleavage with mixed kinetic control by electron transfer and follow-up bond breaking, whatever the scan rate. ... 

Reduction of sulphonium salts polarographic half-wave potentials, Ey. ref. [54], in water cyclic voltammetry peak potentials, Ep ref. [55], in acetonitrile at glassy carbon, scan rate 50 mV s. ... 

Phenols show a two-electron oxidation wave on cyclic voltammetry in acetonitrile at a less positive potential than for the con-esponding methyl ether (Table 6.5) or a related hydrocarbon. Phenol radical-cation is a strong acid with pKg ca. -5 in water [93], so the two-electron oxidation wave for phenols is due to formation of a phenoxonium ion such as 13, where the complete oxidation process is illustrated for 2,4,6-tri-tt rf-butylphenol. Phenoxide ions are oxidised at considerably less positive potentials than the conesponding phenol. They give rise to a one-electron wave on cyclic voltammetry in aqueous acetonitrile or in aqueous ethanol containing potassium hydroxide. 2,4,6-Tri-/ert-butyiphenoxide ion is reversibly oxidised to the radical in a one-electron proces.s with E° = -0.09 V V5. see. The radical undergoes a further irreversible one-electron oxidation with Ep = 1.05 V vs. see on cyclic voltammetry forming the phenoxonium ion which reacts with water [94J. 

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