Kinetics and mechanism of the substitution of aquapentacyanoferrate(III) by cytosine, cytidine and cytidine-5′-monophosphate

Add time:08/05/2019    Source:sciencedirect.com

Kinetic, thermodynamic and spectral data are reported for the formation of low spin d5 pentacyanoferrate(III) complexes of the type Fe(CN)5L starting from Fe(CN)5H2O2− for L=cytosine, cytidine and cytidine-5′-monophosphate. The complexes exhibit strong ligand-to-metal charge-transfer bands in the visible region. In the presence of excess L, the pseudo-first-order rate constant exhibits the behaviour kobs=kf[L]+kd for the overall reaction . The temperature and pressure dependence of kf and kd, as well as of the overall equilibrium constant K (=kf/kd), were studied. The positive values of ΔS‡ and ΔV‡ for both reaction steps suggest the operation of a dissociatively activated mechanism. The results are discussed in comparison to other data for related substitution reactions reported in the literature.

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