Sulfinate ions as nucleophiles

Okuyama, Tadashi

doi:10.1002/9780470772270.ch22

Cited by 6 publications

(1 citation statement)

References 101 publications

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“…A similar situation is found for inorganic ions . Given the fact that sulfinates are considerably less nucleophilic than thiolates, it is surprising that ArSO 2 − reacts with HOCl with rate constants that are several orders of magnitude larger than those for thiolates …”

Section: Discussionmentioning

confidence: 54%

Reactive Sulfur Species: Kinetics and Mechanism of the Oxidation of Aryl Sulfinates with Hypochlorous Acid

2009

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The mechanism of oxidation of ArSO(2)(-) (PhSO(2)(-) and 5-sulfinato-2-nitrobenzoic acid = TNBO(2)(1-/2-)) with HOCl/OCl(-) has been investigated using the kinetic method. In contrast to previous reports for PhSO(2)(-) (for which it was suggested that OCl(-) and not HOCl was the reactant), the reaction proceeds through a conventional pathway: nucleophilic attack by ArSO(2)(-) on HOCl with concomitant Cl(+) transfer to give a sulfonyl chloride intermediate (ArSO(2)Cl), which we have identified spectrophotometrically. Remarkably, the rate constant for the reaction of HOCl with ArSO(2)(-) is on the order of 10(9) M(-1) s(-1), larger than the rate constants for corresponding thiolates, and is nearly diffusion-controlled. In contrast, the rate constant for the reaction of OCl(-) with ArSO(2)(-) is approximately 7 orders of magnitude smaller.

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Section: Discussionmentioning

confidence: 54%