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Issue 6, 1981
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Water–ammonia exchange at amminerhodium(III) complexes in aqueous ammoniacal solution

Sijbe Balt  and  Andries Jelsma 

Abstract

The kinetics of water–ammonia exchange at trans-[Rh(NH3)4(OH)2]+ and [Rh(NH3)5(OH)]2+ have been studied in aqueous ammoniacal solution. The reaction of trans-[Rh(NH3)4(OH)2]+ with ammonia to form [Rh(NH3)5(OH)]2+ has been studied in the temperature range 68–90 °C. The pH dependence of the observed rate constant indicates H2O to be the leaving group. The kinetics could be interpreted in terms of the usual Eigen–Wilkins interchange mechanism, with a more associative character than cobalt(III). The reaction of [Rh(NH3)5(OH)]2+ with ammonia has been studied in the temperature range 112–142 °C, where the reaction results in an equilibrium mixture of [Rh(NH3)5(OH)]2+ and [Rh(NH3)6]3+. The equilibrium constant has been determined spectrophotometrically and kinetically. The forward reaction is pH-independent. The reverse reaction, which gives a small contribution to the overall rate, is base-catalysed. These results can be explained by a direct interchange of OH– and NH3 or by the conjugate-base mechanism.

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Article type: Paper
DOI: 10.1039/DT9810001289
Citation: J. Chem. Soc., Dalton Trans., 1981,0, 1289-1293
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    Water–ammonia exchange at amminerhodium(III) complexes in aqueous ammoniacal solution

    S. Balt and A. Jelsma, J. Chem. Soc., Dalton Trans., 1981, 0, 1289
    DOI: 10.1039/DT9810001289

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