Abstract
The complex cation [ethylenebis(biguanide)]silver(III), [Ag(H 2L)] 3+, and its conjugate bases, [Ag(HL)] 2+ and [AgL] + oxidise NH 2OH quantitatively to N 2O in the pH range 3.00–7.30, themselves being reduced to Ag(I). Free ethylenebis(biguanide) was recovered in near-quantitative yield. The reactions are first-order in both [complex] and total hydroxylamine concentration. The reaction proceeds through three parallel paths: [Ag(H 2L)] 3+NH 2OH ( k 1), [Ag(HL)] 2+NH 2OH ( k 2) and [AgL] +NH 2OH ( k 3), where k 1, k 2 and k 3 are 20.1, 12.5 and 4.35 dm 3 mol −1 s −1, respectively, at 25.0 °C and I=1.0 mol dm −3 (NaNO 3). No silver(I)-catalysed path was detected and the reactions appear to be inner-sphere in nature.
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