Summary
Rate constants are reported for mercury(II)-catalysed aquation of thetrans-[Rh(en)2Cl2]+, [Cr(NH3)5Cl]2+, andcis-[Cr(NH3)4(OH2)Cl]2+ cations in water and in methanol-, ethanol-, and acetonitrile-water solvent mixtures. In the case oftrans-[Rh(en)2Cl2]+, the dependence of rate constants on mercury(II) concentration indicates reaction through a binuclear (Rh-Cl-Hg bridged) intermediate. The dependence of the equilibrium constant for the formation of this intermediate and of its rate constant for dissociation (loss of HgCl+) on solvent composition have been established. With the aid of measured solubilities, published ancillary thermodynamic data, and suitable extrathermodynamic assumptions, the observed reactivity trends for these mercury(II)-catalysed aquations are dissected into initial state and transition state components. The reactivity patterns for these three complexes are compared with those for mercury(II)-catalysed aquation of other chloro-transition metal complexes, particularlycis-[Rh(en)2Cl2]+, [Co(NH3)5Cl]2+, and [ReCl6]2−.
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Adeniran, A.O., Baker, G.J., Bennett, G.J. et al. Initial state and transition state contributions to reactivity in mercury(II)-catalysed aquation of thetrans-[Rh(en)2Cl2]+, [Cr(NH3)5Cl]2+, andcis-[Cr(NH3)4(OH2)Cl]2+ cations in binary aqueous solvent mixtures. Transition Met Chem 7, 183–187 (1982). https://doi.org/10.1007/BF01035839
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DOI: https://doi.org/10.1007/BF01035839