Preparation, characterization and crystal structures of manganese(II), iron(III) and copper(II) complexes of the bis[di-1,1-(2-pyridyl)ethyl]amine (BDPEA) ligand; evaluation of their DNA cleavage activities

Abstract.

The synthesis of a new tetrapyridyl ligand, bis[di-1,1-(2-pyridyl)ethyl]amine (BDPEA), is described. Complexation of this ligand with manganese(II), iron(III) or copper(II) chlorides afforded mononuclear complexes: Mn(BDPEA)Cl₂ (1) [Fe(BDPEA)Cl₂]Cl (2) and [Cu(BDPEA)Cl]Cl (3). In all cases, BDPEA is coordinated to the metal center by three pyridine nitrogen atoms and the secondary amine. The geometrical environments around the metals in Mn(BDPEA)Cl₂ and [Fe(BDPEA)Cl₂]Cl are best described as distorted octahedrals and in [Cu(BDPEA)Cl]Cl as a slightly distorted square pyramid. The DNA cleavage activities of manganese(II), iron(III) or copper(II) complexes of both BDPEA and another tetrapyridyl ligand, bis[di(2-pyridyl)methyl]amine (BDPMA), in the presence of an oxidant (H₂O₂) or a reducing agent (ascorbate) with air, are reported. The iron(III) complexes exhibited significantly enhanced efficiencies, compared to copper(II) complexes. [Fe(BDPEA)Cl₂]Cl is found to be the most active DNA cleaver, in agreement with a better stability of BDPEA in oxidizing conditions.