The anomalous paramagnetism of iron(III) NN-dialkyldithiocarbamates

Abstract

The magnetic moments of a series of 19 NN-disubstituted dithiocarbamates of iron(III), [Fe(S₂C.NR?R")₃], are anomalous in that their behaviour is neither "high-" nor "low-spin". Values of μ_eff. at room temperature lie between 2.62 and 5.83 B.M., the datum for each compound depending on the chemical nature of the substituents R' and R". This anomalous situation persists in benzene or chloroform solution. Cryoscopic and ebullioscopic molecular weight determinations establish that all the compounds are monomeric, which excludes the possibility that the magnetic behaviour arises from the presence of antiferromagnetic exchange interactions of either the inter- or intra-molecular type. These observations strongly support the early and generally overlooked work of Cambi who in 1932 proposed a thermal equilibrium between "magnetic isomers" of spins S = ½ and S = 5/2 to account for the origin of the magnetic anomaly.