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• W2061376095 abstract "Interactions of hydrazines N2H4X+ (X = H or Ph) with tri-, tetra- and penta-chelated ruthenium(III)–aminopolycarboxylic acid complexes giving the respective monomeric hydrazinium (RuIII–N2H4X+) adducts have been investigated by potentiometry, spectrophotometry and voltammetry in aqueous acidic solution at 25 °C. The deprotonation and metal hydrolysis constants of the complexes and their N2H4X+ adducts in 0.1 M Na2SO4 solution were determined. At pH 2.8, the complexes exhibited a quasi-reversible one-electron reduction wave of RuIII → RuII in sampled dc in the potential range between −0.16 and −0.37 V vs. SCE, while their hydrazinium adducts obtained in situ by adding an excess of N2H4X+ showed an additional two-electron reduction wave assigned to RuIII–N2H4X+ → RuI–N2H4X+ in the potential range of −0.02 to −0.35 V vs. SCE. The species RuI–N2H4X+ on successive decomposition and hydrolysis give one mole of each of NH3, NH2X and ruthenium(III) species. Further, the RuIII–N2H4X+ complexes have been used as electro-catalysts for the reduction of N2H4X+ to NH3 and NH2X at a mercury pool cathode in acidic solutions of pH 1.9 and 2.8. The quantity of ammonia produced in all cases is linear with time. The E1/2 of RuIII–N2H4X+ → RuI–N2H4X+ and the turnover number are correlated with the sigma basicity (ΣpKa) of the aminopolycarboxylic acids and the results are discussed in terms of the hydrolytic tendency of the metal, the number of co-ordinating groups and the steric repulsion caused by the increase in size of the aminopolycarboxylic acid." @default.
• W2061376095 created "2016-06-24" @default.
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• W2061376095 date "2000-01-01" @default.
• W2061376095 modified "2023-09-23" @default.
• W2061376095 title "Ruthenium(III)–aminopolycarboxylato complexes active for the reduction of the N–N bond of hydrazine and phenylhydrazine in aqueous acidic media" @default.
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• W2061376095 doi "https://doi.org/10.1039/a908338c" @default.
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