PHOTOAQUATION OF CIS-DICHLOROBIS(1,10-PHENANTHROLINE)CHROMIUM(III) AND THE PHOTOCHEMICAL AND THERMAL-REACTIONS OF THIS COMPLEX WITH NATIVE CALF-THYMUS DNA

The photoaquation of the title compound [cis-Cr(phen)(2)Cl-2(+)] has been studied using high performance liquid chromatography. Both monoaquo [cis-Cr(phen)(2)Cl(OH2)(2)(2+)] and diaquo [cis-Cr(phen)(2)(OH2)(2)(3+)] products are formed, and the quantum efficiency for the loss of starting material in Tris buffer (pH 7) under argon and oxygen is 0.010 +/- 0.001 and 0.0026 +/- 0.0002, respectively. The presence of deoxyguanosine (dG) increases the rate of loss, as much as twofold under argon, but only the rate of diaquo product formation is enhanced by the nucleoside. The dG effect is attributed to reductive quenching of the cis-Cr(phen)(2)Cl-2(+) excited state by the base. Equilibrium dialysis studies indicate that both cis-Cr(phen)(2)Cl-2(+) and cisCr(phen)(2)(OH2)(2)(3+) minimally associate with calf-thymus DNA. However, photolyses of cis-Cr(phen)(2)Cl-2(+) with the nucleic acid yield a mixture of unidentified covalent adducts. The diaquo complex also forms covalent adducts with DNA in the absence of light. Photolyses of the cis-Cr(phen)(2)Cl-2(+) with polyribonucleotides indicate a clear preference for covalent binding to the purines.