Synthesis and co-ordination chemistry of 1,5,9-triazacyclododecane monosubstituted with imidazole and pyrazole

Abstract

The potentially tetradentate ligands 1-(imidazol-4-ylmethyl)- (L¹), 1-(1-methylimidazol-2-ylmethyl)- (L²) and 1-(pyrazol-3-ylmethyl)-1,5,9-triazacyclododecane (L³) have been synthesized; L¹ was isolated as the tetrahydrochloride, L¹·4HCl. The basicity constants of L¹ and L³ have been determined by potentiometry at 25 °C in NaCl. The co-ordination chemistry of L¹ and L³ toward some 3d metal ions has been investigated and the complexes [ML³(Cl)]Y (M = Mn or Fe, Y = BPh₄; M = Ni, Y = BF₄) and [ML(ClO₄)]BPh₄ (M = Co, L = L³; M = Cu or Zn, L = L¹ or L³) have been isolated and characterized. The structures of the iron(II) and nickel(II) complexes of L³ have been determined by single-crystal X-ray analyses. Both contain dimeric [{ML³(Cl)}₂]²⁺ complex cations in which each metal ion is six-co-cordinated by four nitrogen donors of one L³ ligand and by two bridging Cl^- ions in an approximately octahedral environment.

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