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
| Autor: | John Burgess, Gareth J. Baker, A. Olabode Adeniran, Gabriel J. Bennett, Michael J. Blandamer, Nilam K. Dhammi, Philip P. Duce |
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| Rok vydání: | 1982 |
| Předmět: |
Aqueous solution
Inorganic chemistry Metals and Alloys Aquation chemistry.chemical_element Dissociation (chemistry) Mercury (element) Inorganic Chemistry Solvent chemistry.chemical_compound Reaction rate constant chemistry Materials Chemistry Physical chemistry Organometallic chemistry Equilibrium constant |
| Zdroj: | Transition Metal Chemistry. 7:183-187 |
| ISSN: | 1572-901X 0340-4285 |
| DOI: | 10.1007/bf01035839 |
| Popis: | 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−. |
| Databáze: | OpenAIRE |
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