Synthesis of a 13-membered macrocyclic tetrathiadioxime and its mono- and tri-nuclear complexes with tetrahedrally co-ordinated palladium(II)

Abstract

2,3-Bis(hydroxyimino)-1,4,7,11-tetrathiacyclotridecane (H₂L) has been prepared from 1,9-dimercapto-3,7-dithianonane and anti-dichloroglyoxime. Only mononuclear complexes with a metal–ligand ratio of 1:2 have been isolated with Ni^II and Co^II; Cu^II and Pd^II form only trinuclear complexes. The reaction of the mononuclear complexes with Cu^II and Pd^II gives heterotrinuclear complexes. Tetrahedral distortion of the 13-membered macrocycle is observed in the paramagnetic [Pd₃(HL)₂]Cl₄ and [Pd₂Ni(HL)₂]Cl₄ compounds. All these complexes are insoluble in common solvents; structures are proposed according to elemental analysis, i.r., and magnetic susceptibility measurements.