Synthesis of non-symmetrically substituted tetraimine macrocyclic complexes of copper(II) and nickel(II)

The non-symmetrically functionalized neutral 6,13-substituted-1,4,8,11-tetraazacyclotetradeca-4,6,11,13-tetraene complexes of copper(II) and nickel(II) were synthesized by mesylation of symmetric diol derivatives in neat, anhydrous pyridine at 0°C. The products of monomesylation were used to obtain macrocyclic copper(II) and nickel(II) complexes substituted with bulky terminal group on one end and thiol functional group on the other. Linear arrangements of two or three macrocyclic units terminally blocked with bulky tris(p-tert-butylphenyl)(4-phenoxy)methane substituents were obtained from monomesylated intermediates. Free ligands obtained by demetallation reaction of neutral copper(II) tetraazamacrocyclic complexes were used for the synthesis of nickel(II) analogs.