Reversible one-electron reduction and

An electrochemical survey of many of these compounds has been reported. Most of the neutral compounds show a reversible one-electron reduction and an irreversible one-electron oxidation whereas the anions (306) exhibit irreversible reduction and quasi-reversible oxidation behaviour.625... 

Electrochemical studies of the series of phosphite and phosphine substituted compounds Os6(CO),2i- ) PR3 (R = OMe, n = 1-6 R = Ph, n = 1-3) 99) are in accord with the predictions of Evans and Mingos. These compounds undergo two well-defined reversible one-electron reductions and one irreversible oxidation (Table III). A correlation has been established between the values of ,/2 for the first wave potential and the number of... 

Complexes 39 exhibit a quasi-reversible one-electron reduction, and the potential of the Mo(V/IV) couple varies by 1.2 V as a function of donor atom complexes with X = SR are more easily reduced than those with X = OR. Variation of the ligand backbone in (L-N3)MoO X-(CH) -X (X = O, S n = 2-4) complexes (40) produces a dramatic... 

Within the large number of multiredox arrays containing metalloporphyrins/covalently bound (conjugate) fullerene-metalloporphyrin dyads have gained enormous interest in the last ten years, mainly due to their potential application as artificial antennae Due to the multiredox behaviour of the fullerenes (up to six reversible one-electron reductions and at least one reversible one-electron oxidation), the porphyrin ligands and the incorporated metals, the assignment of electron-transfer steps in such systems is difficult. Recently, spectroelectrochemical characterisation has been carried out on a number of fullerene-[(TPP)Co] dyads shown in Scheme 4.3, which exhibit rather complex redox behaviour (Figure 4.19). 

Electrochemical studies have shown that each Fe3MoS4 " cubane-like cluster exhibits a reversible one-electron reduction and oxidation process, giving rise, for exai le, in the dimeric species [Fe6Mo2Sg(SR)9] to 1-/2-, 2-/3-, 3-/4- and 4-/5- couples. Fe... 

Figure 4. The reversible one-electron reduction and oxidation reactions of nitroxyl free radicals.

Electrochemical synthetic methods are usually easily controllable, selective and simple. The current density or potential of the working electrode can be easily adjusted resulting in a desired rate and/or the desired products formed. Fullerenes, which can undergo as many as six reversible one- electron reductions and one... 

Although the trinuclear core formally contains vanadium(lll) and vanadium (IV) ions, all are equivalent suggesting that the unpaired electron(s) are delocalized. The paramagnetic trimetallic center also has an unusual effect on the chemical shifts of a-protons of the dithiocarbamate ligands in the NMR spectrum, which can be shifted downfield as far as 6 10.7 ppm. The clusters are redox active and undergo reversible one-electron reduction and oxidation processes (697). 

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