Light-activated generation of nitric oxide (NO) and sulfite anion radicals (SO3 center dot-) from a ruthenium(II)nitrosylsulphito complex

This manuscript describes the preparation of a new Ru(II) nitrosylsulphito complex, trans-{[}Ru(NH3)(4)(isn)(N(O)SO3)](+) (complex 1), its spectroscopic and structural characterization, photochemistry, and thermal reactivity. Complex 1 was obtained by the reaction of sulfite ions (SO32-) with the nitrosyl complex trans {[}Ru(NH3)(4)(isn)(NO)](3+) (complex 2) in aqueous solution resulting in the formation of the N-bonded nitrosylsulphito (N(O) SO3) ligand. To the best of our knowledge, only four nitrosylsulphito metal complexes have been described so far (J. Chem. Soc., Dalton Trans., 1983, 2465-2472), and there is no information about the photochemistry of such complexes. Complex 1 was characterized by spectroscopic means (UV-Vis, EPR, FT-IR, H-1- and N-15-NMR), elemental analysis and single-crystal X-ray diffraction. The X-ray structure of the precursor complex 2 is also discussed in the manuscript and is used as a reference for comparisons with the structure of 1. Complex 1 is water-soluble and kinetically stable at pH 7.4, with a first-order rate constant of 3.1 x 10(-5) s(-1) for isn labilization at 298 K (t(1/2) similar to 373 min). Under acidic conditions (1.0 M trifluoroacetic acid), 1 is stoichiometrically converted into the precursor complex 2. The reaction of hydroxide ions (OH-) with 1 and with 2 yields the Ru(II) nitro complex trans-{[}Ru(NH3)(4)(isn)(NO2)](+) with second-order rate constants of 2.1 and 10.5 M-1 s(-1) (at 288 K), respectively, showing the nucleophilic attack of OH- at the nitrosyl in 2 (Ru-NO) and at the nitrosylsulphito in 1 (Ru-N(O)SO3). The pK(a) value of the -SO3 moiety of the N(O)SO3 ligand in 1 was determined to be 5.08 +/- 0.06 (at 298 K). The unprecedented photochemistry of a nitrosylsulphito complex is investigated in detail with 1. The proposed mechanism is based on experimental (UV-Vis, EPR, NMR and Transient Absorption Laser Flash Photolysis) and theoretical data (DFT) and involves photorelease of the N(O)SO3- ligand followed by formation of nitric oxide (NO center dot) and sulfite radicals (SO3 center dot-, sulfur trioxide anion radical). (AU)