Abstract:
The silver(I) complex of a 15-membered macrocyclic ligand with an N₃S₂ donor set (L¹) has been prepared by
the reaction of 2,6-diacetylpyridine with 1,8-diamino-3,6-dithiaoctane in the presence of silver(I) ions.
A reduced form (L²) of the ligand, in which the imine groups are converted to amines, was prepared by
the reduction of the silver(I) complex by sodium borohydride. The ligand L² has been characterised by various
spectroscopic techniques and the copper(II) complex has been prepared. The metal complexes of L¹ and L²
have been characterised by electrospray mass spectrometry and UV-visible spectroscopy. The copper(II)
complex of L¹ has been synthesised from [AgL¹]⁺ via metal exchange. [CuL¹](CIO₄)₂crystallises in the orthorhombic
space group Pna2₁ with a= 14,374(5)Å, b = 12.947(3)Å, C = 11.824(3)Å with Z =4. The geometry
about the metal centre approximates trigonal bipyramidal with the pyridinyl nitrogen and the sulfur
donors in the equatorial positions and the imine nitrogen donors in the axial positions. Metal ion exchange
and the relative stabilities of metal complexes of the macrocyclic ligands were studied by electrospray mass
spectrometry.
