Nuclear magnetic resonance spectra and redox behaviour of transtion metal dithiocarbamates

Abstract

From a study of the isotropic proton hyperfine interaction constants for a series of metal dithiocarbamates, and their redox behaviour, it is shown that for iron(111) and manganese(111) dithiocarbamates there is a simple relationship between E1/2 and the NCH2 proton hyperfine interaction constant in the 6Al state. Hence the redox process for these compounds is inferred to take place through the nitrogen atom.

Spin state dependent redox properties of the [Fe(III)(X-sal)2trien]+ spin-equilibrium system in solution

“…Caled for FeC20H22N6O6-0.75H2O: C, 46.75; H, 5.00; N, 16.36; Fe, 10.87. Found: C, 46.84; , 4.40; N, 16.26;Fe,10.42. Physical Measurements.…”

Ligand Radioisotopic Exchange Reaction of Diethyldithiocarbamato Complexes of Fe (III), Co(lll) and Ni(ll) in Dioxane and Dimethylformamide

“…Ligands in dtc complexes may show an electron shift from nitrogen to sulphur atoms [5,13,14]. energy for structure which can be represented by the mechanism Sj^j model (e. g. a Square pyramid), the Sj^j reaction mechanism will lead to a considerable loss of the stabihzation energy, and, therefore, will proceed slowly [16].…”

“…It has been demonstrated[14] that the extent of the d-electron delocalization from the metal to the dedtc ligands increases as the crystal field strength increases. This effect can be rationalized in the terms of the canonical structures I and II.…”

“…This effect can be rationalized in the terms of the canonical structures I and II. Structure I predominates in strong field complexes, while structure II predominates when crystal field is weak[14]. If Co[dedtc]3 revealed the structure I, the cobalt would coordinate additional ligand and, therefore, the total reaction mechanism might include a small contribution from the associative mechanism.…”