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The final product from controlled-potential reduction of aqueous solutions of trans-[Rh(en)2Cl2]+(where en = ethylenediamine), under an argon atmosphere, has been shown to be trans-[Rh(en)2H(OH)]+. The pseudo-acid–base equilibrium (i) is shown to operate in solutions which are strongly alkaline (pH > 12). In the absence of RhIII–H + OH–⇌ RhI+ H2O (i), oxygen, aqueous solutions of trans-[Rh(en)2H(OH)]+ are stable toward both acid and base (0 < pH < 12) at room temperature : in the presence of oxygen, no reaction is observed in acidic solutions whereas rapid reactions are observed in basic solutions, giving initially the hydroperoxorhodium(III) complex [Rh(en)2(OH)(OOH)]+, which on concentration yields the blue superoxo-bridged rhodium(III) dimer [(H2O)(en)2RhO2Rh(en)2(H2O)]5+. Mechanisms of these reactions are discussed.
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Gillard et al. (1970) studied this question.
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