Electrochemical reduction of trans-[Rh(en)2Cl2]+ and subsequent reactions with oxygen
- 1 January 1970
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc. A
- p. 3126-3130
- https://doi.org/10.1039/j19700003126
Abstract
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.Keywords
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