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 μeff. 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 = � and S = 5/2 to
account for the origin of the magnetic anomaly.
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