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The magnetic behaviour of some trivalent iron complexes of N,N-dialkyldithiocarbamic acids

The majority of octahedral complexes of trivalent iron exhibit simple Curie or Curie-Weiss law magnetic behaviour and can be classified as either high-spin or low-spin. In high-spin complexes the 6A1 and in low-spin complexes the 2T2 term lies lowest. Whether the 6A1 or the *Tz term is the ground-state depends on the magnitude of the ligand field. When the ligand field is sufficiently strong the 2T2 will cross the 6A1 term to become energetically the more stable of the two. A number of N,N-dialkyldithiocarbamato complexes of iron(111) have magnetic moments intermediate between high-spin and low-spin values.1 The variation of the magnetic susceptibility with temperature indicates the presence of a temperaturedependent equilibrium between highand low-spin states in the same complex. In these compounds the ligand-field strength is very close to the 6A1-2T2 crossover. The energy separation between the highand low-spin states becomes very small so that the relative population of them is temperature-dependent. The magnetic susceptibility a t the 6A1-2T2 crossover of a number of N.N-dialkyldithiocarbamates of iron(111) was measured a t various temperatures by Ewald et al.2 Ewald et al. derived an expression (1) for the magnetic moment by applying van Vleck's equation to the energy level pattern appropriate to the d5 configuration near the crossover