Maria G. Santana-Marques

Structural characterisation and DFT studies of (Cr(cyclam)(O-dmso)Cl) 2 : a new precursor complex towards potential DNA intercalators

The synthesis and structural characterisation of the complex [Cr([14]aneN4)(O -dmso)Cl](PF6)2/dmso is reported. The structural studies were carried out in gas-phase by electrospray mass spectrometry (ESMS) and in the solid state by single crystal X-ray diffraction. The metal complex shows a distorted octahedral coordination environment with the macrocycle adopting a folded cis -V conformation. The angle Naxial � /Cr� /Naxial deviates by only 128 from the ideal value of 1808 for a perfect octahedron indicating that there is a good match between the size of the macrocyclic cavity and the size of Cr(III) ion. The ESMS shows that the complex loses a proton with concomitant opening of the [14]aneN4 ring to give the [Cr([14]aneN4-H)(dmso)Cl] � ion with a CH2� /CH� / pendant chain. This group interacts with dmso leading to the loss of this ligand and to the formation of the [Cr([14]aneN4-H)Cl] � ion, which has the highest relative abundance (100%). DFT calculations reproduce the geometry of the paramagnetic complex and are consistent with its electronic spectrum. # 2003 Elsevier Science B.V. All rights reserved.