Oxidovanadium(IV) complexes containing ligands derived from dithiocarbazates – Models for the interaction of VO2+ with thiofunctional ligands

The tetragonal–pyramidal VO2+ complexes [VO{(RSC–S)N–NX}2] (1–6) were synthesised by the reactions of VO(OCHMe2)3 with the dithiocarbazate ligands RSC(S)–NH–NX, where X = cyclo-pentyl, cyclo-hexyl or 4-Me2N–C6H4–CH, and R = CH3 or CH2C6H5. The compounds were characterised by elemental analysis, IR- and mass spectrometries, and in cases of compounds 1, 3, 4 and 5, by X-ray diffraction. The chiral compound 4 (X = cyclo-hexyl, R = CH2C6H5) crystallises in the C configuration. In compound 5, the VO moiety is disordered (83.3:16.7%) with respect to the plane spanned by the four equatorial ligand functions.

Dithiocarbamates form complexes with the VO2+ ion in redox-interaction with VO(OiPr)3, in which the ligand reacts out of its sulfhydryl tautomeric form. The geometry is in-between square–pyramidal and trigonal–bipyramidal.Figure optionsDownload as PowerPoint slide