Abstract
The kinetics of oxygenation of [(PDTA)Ru III(H 2O)] − (complex 1) to [(PDTA)Ru V(O)] − (complex 2) by KHSO 5 was studied spectrophotometrically by monitoring the appearance of the characteristic oxo peak (393 nm, ϵ max 393 = 8200) at a fixed pH 6.0 and ionic strength 0.2 M (NaClO 4). The time course of the oxygen atom transfer from complex 2 to PPh 3 was investigated by following the disappearance of characteristic oxo-peak of the oxo-complex 2 as a function of PPh 3 concentration and temperature (30–50 °C) at a fixed pH 6.0 and ionic strength of 0.2 M (NaClO 4). Activation parameters for both the oxygenation of complex 1 to complex 2 and oxygen atom transfer from complex 2 to PPh 3 were calculated and probable mechanisms for both reactions proposed.
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