Electrochemical reduction and oxidation of cobalt(III) dithiocarbamates

Electrochemical Examination of Mixed-Ligand Cobalt(III) Complexes with Tetraazamacrocyclic Ligand and Heterocyclic Dithiocarbamates

“…The more pronounced separation of the basic peaks with stronger disturbance of the symmetry in order 4-> 3-> 2-Mepipdtc ligands, is probably due to the influence of shifting the methyl group and its positive inductive effect toward the > NCS 2 group. The CVs of the corresponding complexes [Co III Rdtc(5-8)cyclam](ClO 4 ) 2 show equality and only one anodic and one cathodic peak is present ( Table 2), but in comparison with the first group of the complexes [Co III Rdtc (1-4)cyclam](ClO 4 ) 2 these peaks are at more negative potentials, i.e., oxidation peak is at À0.72 V and reduction peak is at À0.78 V.…”

“…3B, C and Table 2). According to the literature data [24] redox reaction Co(III)=Co(II) of cobalt(III) dithiocarbamate complexes occurs at high cathodic potentials in nonaqueous solutions, while oxidation of Co(III) to Co(IV) species is at high anodic potentials [25]. Therefore, the absence of any peaks should mean that the redox reactions in the case of [Co III Rdtc(1-8)cyclam] 2þ complexes are ruled out.…”

“…Dithiocarbamato ligands have capability to stabilize metal ions in unusually high oxidation states [1][2][3][4]. They have high tendency of MS 4 and MS 6 coordination and act as almost uninegative bidentate ligands coordinating through both the sulfur atoms.…”

Electrospray ionization of neutral metal dithiocarbamate complexes using in-source oxidation

“…No other ions were reported. C final oxidation product 26,32,42 is seen at m/z 858; however, the et 4 C ion at m/z 510, attributed to steric hindrance of the octahedral geometry of Co(III) et 2 dtc 3 and to differences in the ion sources employed. The ion at m/z 471 may be due to the loss of S from the Co(IV) et 2 dtc 3 C ion.…”

“…The preparation of Mn(III) et 2 dtc 3 was based on Hendrickson et al 24 and Cu(II) et 2 dtc 2 was prepared according to Thorn and Ludwig. 18 The synthesis of Ni(II) et 2 dtc 2 was based on Hendrickson, et al 25 and that of Co(III) et 2 dtc 3 was based on Bond et al 26 The purity of the ligands and complexes was confirmed using thin-layer chromatography and the structures of the piperidinedithiocarbamate, methylpiperazinedithiocarbamate and sodium di-n-butyldithiocarbamate and the Ni(II) et 2 dtc 2 and Co(III) et 2 dtc 3 complexes were confirmed using NMR spectroscopy.…”