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Origin of the oxygen in the oxidation of triphenylphosphine by potassium persulfate—application of the 18O isotope effect in 31P NMR

✍ Scribed by John M. Risley; Robert L. Van Etten

Publisher
John Wiley and Sons
Year
1984
Tongue
English
Weight
300 KB
Volume
16
Category
Article
ISSN
0538-8066

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✦ Synopsis

Abstract

Potassium persulfate oxidizes triphenylphosphine to triphenylphosphine oxide in 60% aqueous acetonitrile. It has been suggested that the oxygen of the product, triphenylphosphine oxide, might originate from solvent water, following nucleophilic attack on an intermediate phosphonium ion. We have investigated the origin of the oxygen in the oxidation of triphenylphosphine by potassium persulfate in 60% aqueous acetonitrile containing 20% [^18^O]water. The product was analyzed by using the ^18^O isotope effect in ^31^P NMR spectroscopy. The magnitude of the ^18^O isotope‐induced shift was determined by synthesizing triphenylphosphine [^18^O]oxide and was found to be 0.038 ppm upfield. The product of the oxidation reaction in 20% [^18^O]water displayed no ^18^O isotope effect. The origin of the oxygen in the oxidation reaction is the persulfate ion, consistent with an alternative mechanism involving nucleophilic attack by water at the sulfur atom of a phosphonium peroxysulfate intermediate.

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