SYNTHESIS OF THE MONOOXORUTHENIUM(V) COMPLEXES CONTAINING THE AMINO POLYCARBOXYLIC ACID LIGANDS EDTA AND PDTA AND THEIR REACTIVITIES IN THE OXIDATION OF ORGANIC SUBSTRATES - X-RAY CRYSTAL-STRUCTURES OF K[RUIII(EDTA-H)CL].2H2O AND K[RUIII(PDTA-H)CL].0.5H2O

The syntheses and characterization of K[Ru(V)=O(EDTA)] (3) and K[Ru(V)=O(PDTA)] (4) are described. The kinetics of the formation of 3 and 4 by the interaction of the corresponding chloro complexes K[Ru(III)(EDTA-H)Cl] (1) and K[Ru(III)(PDTA-H)Cl] (2) with the oxygen atom donor NaOCl was investigated in the temperature range 30-50-degrees-C. The activation parameters of the oxygenation reaction of 1 and 2 to 3 and 4, respectively, are consistent with an associatively activated process. The O atom transfer reaction from 3 and 4 to the unsaturated and saturated hydrocarbons were studied spectrophotometrically in the temperature range 30-50-degrees-C by following the disappearance of the characteristic oxo peak of the complexes at 393 nm and by product analysis. The activation parameters for the oxidation of the substrates corresponding to the rate-determining oxygen atom transfer step were determined, and a suitable mechanism was proposed. The crystal and molecular structures of the precursor complexes 1 and 2 were determined using single-crystal X-ray diffraction technique.