The nitrosodisulfonate anion radical, ˙NO(SO3)22−, a single electron oxidant, reacts rapidly with the 2e− metal-based reductants, Sn(II) and Ge(II)
(k
= 104–105 M−1 s−1), less rapidly with sulfite (k
= 0.24 M−1 s−1) and very slowly (10−3–10−2 M−1 s−1) with the nonmetal-based donors, H2AsO3−, SbIII(tartrate), hyponitrite, and hypophosphite. Reductions yield the product HON(SO3)22−. Kinetic profiles exhibit no irregularities attributable to generation or loss of a transient on a time scale comparable to the principal conversion, indicating that rates are determined by the original 1e− transfer and that the “follow-up” step is rapid. Reductions by sulfite (pH 4.2–8.6) are retarded by partial conversion to HSO3−, whereas those by Sn(II) and Ge(II)
(in 0.1–1.0 M H+) are accelerated by H+. Rates for Sn(II) are markedly enhanced by chloride, suggesting stabilization of intervening chloro-ligated Sn(III).
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