Reaction of K2[RuCl5(H2O)] with N,N′-dimethyl-N,N′-bis(2-pyridylmethyl)ethylenediamine (L1) in ethanol gave cis-[RuIIIL1Cl2]+and then cis-[RuIIIL1(Cl)(H2O)]2+upon reaction with AgIin water. The structure of cis-[RuIIIL1(Cl)(H2O)][ClO4]2·2H2O has been established by X-ray crystallography: space group Pbca, a = 10.863(1), b = 21.548(2), c = 21.912(2) Å. The measured Ru-Cl and Ru-OH2distances are 2.307(4) Å and 2.070(9) Å respectively. A cyclic voltammogram of cis- [RuIIIL1(Cl)-(H2O)]2+in 0.1 mol dm-3CF3CO2H shows three reversible/quasi-reversible couples at 1.29, 0.93 and 0.23 V vs. saturated calomel electrode assigned to the couples RuV-RuIV, RuIV-RuIIIand RuIII-RuII. The complex cis-[RuIIIL1(Cl)(H2O)]2+is an active catalyst for the electrochemical oxidation of alcohols and tetrahydrofuran. The second-order rate constant for the oxidation of benzyl alcohol by electrochemically generated cis-[RuVL1(Cl)O]2+is estimated to be 8.4 × 104dm3mol-1s-1.
|Number of pages||6|
|Journal||Journal of the Chemical Society, Dalton Transactions|
|Publication status||Published - 1 Dec 1991|
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