Pressure effects on the rates of Hg-assisted chloride release from some [CrCl(diamine)(triamine)] complexes |
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Authors: | Donald A House Rudi van Eldik |
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Institution: | a Department of Chemistry, University of Canterbury, Christchurch, New Zealand b Institute for Inorganic Chemistry, University of Witten Herdecke, 58448, Witten, Germany |
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Abstract: | The rate of Hg2+-assisted chloride release from several mer-CrCl(diamine)(triamine)]2+ complexes has been measured as a function of pressure, Hg2+ concentration and temperature. The calculated activation volumes are independent of Hg2+] and temperature and kinetic parametes 104 kHg (25 °c) (M−1 s−1), ΔH‡ (kJ mol−1), ΔS‡ (J K−1 mol−1), ΔV‡ (cc mol−1) are: (en)(dpt): 6.44. 75.5, −52, −5.0; (ibn)(dpt): 5.81, 89.5, −6, −0.03; (Me2tn)(dpt): 22.2, 84.9, −11, −0.5; (tn)(dpt): 29.1, 87, −1, +0.3; (en)(2,3-tri): 1.94, 87.0, −24, −5.7; (en)(Medpt): 0.417, 94.6, −11, −0.8; (tn)(Medpt): 9.14, 98.3, +26, +1.8. |
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Keywords: | Kinetics mechanism Pressure effect Chromium complexes Polydentate amine complexes |
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