TRIAZOLATE-CONTAINING MACROCYCLIC TRANSITION-METAL COMPLEXES DERIVED FROM BIS(3-AMINOPROPYL)AMINE AND 3,5-DIACYL-1,2,4-TRIAZOLES

Template 1:1 condensation of 3,5-diacetyl- or 3,5-diformyl-1,2,4-triaz ole with bis(3-aminopropyl)-amine in the presence of 1 equivalent of L iOH and M(ClO4)2 (M = Ni, Cu, Co or Pb) produces mononuclear tetraaza 14-membered macrocyclic Schiff-base metal(II) complexes [ML]ClO4 {L = 12-hydroxy-2,12-dimethyl- or -hexaazabicyclo[11.2.1]hexadeca-2,13,15-t rienate}. These compounds are derived from the expected diimino macroc yclic complexes by formal addition of water across one of the azomethi ne bonds. Reduction of the Schiff-base complexes with sodium tetrahydr oborate provides the corresponding saturated tetraaza macrocyclic comp lexes. Both sets of compounds were identified and studied by liquid se condary ion mass spectrometry.