The relativistic multiple scattering Xα method has been applied in order to calculate the eigenvalues and the charge densities of cis and trans diaminodichloroplatinum(II). The activity of the cis isomer as an antitumor agent is discussed in terms of the possible modes of coordination of certain fragments of the DNA molecule through the LUMO state of the cis Pt complex. Although possible, coordination of the trans isomer is rendered unlikely as a result of possible strain effects.