Polyamine ligands. I. The stereochemistry of transition metal complexes with the ligand 1,8-Bis(2'-pyridyl)-3,6-diazaoctane

Abstract

The new polyamine ligand 1,8-bis(2'-pyridyl)-3,6-diazaoctane has been synthesized for the first time by the reaction between 2-vinylpyridine and ethyl-enediamine. The ligand could not be distilled without decomposition and hence it was purified by converting it into the crystalline copper(11) perchlorate complex, from which the ligand was liberated by the reaction with sodium sulphide solution. The pure ligand was obtained in an overall yield of 28%, based on starting materials. The complexes formed by the ligand with the metal ions copper(11), nicke1(11), palladium(11), zinc(11), and cobalt(111) were isolated and characterized by physical measurements of their conductance in solution, magnetic moments, infrared and electronic absorption spectra. The ligand adopts the planar-N₄ configuration around the metal ion in the complexes with copper(11), nicke1(11), and palladiurn(11), whereas it probably adopt's a tetrahedral-N₄ configuration around the zinc(11) complex ion. The nickel(11) perchlorate complex is diamagnetic in the solid state and it most likely contains the metal ion in square-planar cordination. When dissolved in coordinating solvents, this complex undergoes a reversible, temperature-dependent equilibrium between diamagnetic and solvated, paramagnetic forms.