Cyclic voltammetry of some ferrocenephanes in acetonitrile

ZnII and CdII Ferrocenechalcogenolate Complexes

“…The latter were determined to arise from consecutive one-electron oxidations of the ferrocene moieties of the known disulfide FcSSFc. [13] This was confirmed by comparison of the CV with that of an authentic sample of FcSSFc. [14] The oxidative cleavage of the zinc ferrocenethiolate and the formation of diferrocenyl disulfide mirrors previous findings on the electrochemical properties of group 11 and 12 metal ferroceneselenolates [8a,8b] in the absence of an insulating linker between the chalcogen centre and the cyclopentadienyl ring.…”

“…[16] With increasing Zn-L bond length (decreasing s-character of the interaction between Zn and ligand L donor atom), a consequent increase in the ∠E-Zn-E is observed. The angles for the selenium congener 3b are similar at N1-Zn1-N2 85.73 (13) and Se1-Zn1-Se2 130.62(2)°(parameters listed refer to one of the two independent molecules in the asymmetric unit). These parameters can be compared with those of the benzeneselenolate complex [(N,N′-tmeda)Zn(SePh) 2 ], with NZn-N 86.3(3) and Se-Zn-Se 125.54(6)°, the latter angle much reduced with the smaller phenyl substituents on the selenium centres.…”

“…The reagents PnPr 3 , [19] Fc 2 S 2 , [14] fc(SeSiMe 3 ) 2 and FcSeSiMe 3 , [8a,8b] were synthesized according to literature procedures. NMR spectra were recorded with either a Varian Inova 400 spectrometer ( 1 H, 13 …”

Direct Electrochemical Determination of Thermodynamic Factors in Aprotic Binary Electrolytes

“…22 would yield a value of = 11.6, which indeed is reasonably consistent with the peak separation of ∼63 mV at ≥5 mM LiClO 4 shown in Figure 5. 20 For LiClO 4 concentrations below 5 mM (at a ferrocene concentration of 0.05 mM), the observed increase in peak separation may be due to several effects and is currently not understood. The kinetic rate constant k 0 and the ratio of diffusion coefficients of ferrocene and ferrocenium depend on the concentration of LiClO 4 as explained in the theoretical part of this work.…”

“…Based on this boundary condition, the following theoretical relations can be derived for the oxidation peak only in the first cycle. 14 The theoretical peak position U p,ox for the first cycle is given by [20] and the peak current by ) and if all other terms are constant, it is possible to determine the mean activity coefficient from the peak potential.…”