On the anomalous magnetic properties of tris(diselenocarbamato)iron(III) compounds

Abstract
An extended magnetic investigation of a series of pseudo-octahedral [Fe(Se2CNR2)3] compounds [R2= piperidino, morpholino, thiomorpholino, Bu2, Et2, (PhCH2)2, (C6H13)2, and MePh] has been made at 90–400 K. Diamagnetic compounds not containing iron, Se(Se2CNEt2)2, Se[Se2CN(CH2Ph)2]2, and (Se2CNMePh)2, have also been isolated and their presence could explain the previously reported low-spin classification of [Fe(Se2CNR2)3] compounds. The reported measurements demonstrate that the magnetic behaviour of these compounds is anomalous, the µ values generally ranging between the limiting values typical for 6A1 and 2T2 states. Treatment of the experimental values by means of van Vleck's equation has enabled the evaluation of the crossover parameters, and a full comparison with the dithiocarbamate derivatives is made. The influence of the substituents on the nitrogen of the ligand on the position of the spin equilibrium is discussed.

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