Copper(II) complexes of 6-hydroxymethyl-substituted tris(2-pyridylmethyl)amine ligands

Three potentially tripodal, tris(2-pyridylmethyl)amine (tpa) ligands with hydroxymethyl substituents, [6-(hydroxymethyl)-2-pyridylmethyl]bis(2-pyridylmethyl)amine (HL1), bis[6-(hydroxymethyl)-2-pyridylmethyl]2-(pyridylmethyl)amine (H2L2), tris[6-(hydroxymethyl)-2-pyridylmethyl]amine (H3L3), have been prepared in good yields. From these ligands, the copper(II) co-ordination complexes [Cu(HL1)Cl]Cl 1, [Cu(H2L2)Cl]X (X = Cl 2 or p-toluenesulfonate 3), [Cu((LBF2)-B-2)][BF4] 4 a complex of a novel macrocyclic anion with a tpa core, [Cu(H3L3)Br0.43Cl0.57](2)[Cu(Br0.43Cl0.57)(2)(Br0.97Cl0.03)(2)] 5 with compositionally disordered bromo and chloro co-ligands, [Cu(H3L3)Br]Br 6 and the unusual trimer [Cu-3{H-3(L-3)(2)}Br][BF4](2) 7 have been synthesized and their spectroscopic and redox properties and crystal structures obtained.