Chelation of iron(II) dithiocarbamates: an electrocatalytic process with an endergonic cross electron-transfer propagation step

The electrocatalysed chelation of the dimethyldithiocarbamate ligand (dtc) in [Fe(η5-C5R5)(CO)2(σ-dtc)](R = H or Me) is shown to involve a dual role of the oxidant in an efficient process involving an endergonic (ΔG° 12 kcal mol–1) cross electron-transfer propagation step; the preparative yields are subject to a ‘specific anion effect’ which controls the importance of the deactivation of the overall chain conversion.