Mössbauer studies of a series of iron(III) dithiocarbamates show: (i) that the iron atom is in an environment with slight distortion from octahedral symmetry, the splitting of the octahedral 2T2 state being less than 150 cm–1, and (ii) that the degree of delocalization of the iron d-electrons depends on the ligand. Estimated values for the d-orbital t2 molecular orbital coefficient are given.