Oxidation of thiols. I. Kinetics and mechanism of oxidation of β-hydroxy-α-thiobenzoyl- p-methoxystyrene by hexacyanoferrate(III) in neutral and weakly alkaline medium

Abstract

The oxidation of β-hydroxy-α-thiobenzoyl- p-methoxy-styrene by hexacyanoferrate(III) follows the rate law(i) ▪ The two pathways showing first order in [Fe(CN) 3− 6] T are believed to proceed by an outer-sphere mechanism, with the acid-independent route involving the thiol form RSH, and in the acid-dependent route the thiolate ion, RS − was encountered. The pathway independent of [Fe(CN) 3− 6] proceeds via the formation of an intermediate [(CN) 5Fe(CNSR)] 4− in which a sulphur-carbon bond is probably formed between the thiolate ion and a coordinated cyano-ligand. No copper(II) ions catalysis was observed.