Summary
The reaction between the title compound, α,β,γ,δ-tetra(p-sulphonatophenyl)porphynatoaquacarbonylruthenate(II), [Ru(TPPS)(CO)(H2O)]4−, and CN- revealed that only the aqua ligand is substituted even in the presence of a large excess of the nucleophile. The pK a1 was spectrophotometrically determined as 13.4(5) (at 33.2 °C) and kinetically as 13.44(5) (at 33.6 °C). The rate of aqua substitution was determined as 89(4)m −1 s −1 at 35.1 °C and the activation enthalpy and entropy as 55.44(1) kJ mol−1 and-27.90(4) J K−1 mol−1, respectively.
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Purcell, W., van der Westhuizen, H.J. & Meyer, H. The substitution kinetics of the aqua ligand by cyanide ions in [Ru(TPPS)(CO)(H2O)]4− . Transition Met Chem 21, 77–80 (1996). https://doi.org/10.1007/BF00166019
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DOI: https://doi.org/10.1007/BF00166019