Abstract
New carbodithioate complexes of the oxovanadium(IV), manganese(II) and manganese(III) ions have been prepared and studied by i.r. and electronic spectral and variable temperature magnetic susceptibility (77K to room temperature) measurements. The carbodithioate ligands, 4-methylpiperazine-1-carbodithioate (4-MPipzcdt) and 4-phenylpiperazine-1-carbodithioate (4-PPipzcdt), were derived from heterocyclic secondary amines. The VO(4-MPipzcdt)2 and VO(4-PPipzcdt)2 complexes possess C4v symmetry; Mn(4-PPipzcdt)2 is tetrahedral and Mn(4-PPipzcdt)3 is octahedral. All exhibit abnormal room temperature magnetic moments and the variable temperature magnetic moments suggest antiferromagnetism for the oxovanadium(IV) and the manganese(II) complexes and the occurrence of low spin (3T1g) ⇌high spin (5Eg) equilibrium in addition to antiferromagnetic interactions in the manganese(III) complex. The spin-spin exchange parameter (-2J) value for the VO(4-MPipzcdt)2 complex has been calculated using variable temperature magnetic susceptibility data.
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