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Mechanism of oxidation of triphenylphosphine, triphenylarsine, and triphenylstibine by potassium peroxodisulfate

✍ Scribed by C. Srinivasan; K. Pitchumani

Publisher: John Wiley and Sons
Year: 1982
Tongue: English
Weight: 456 KB
Volume: 14
Category: Article
ISSN: 0538-8066
DOI: 10.1002/kin.550141204

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✦ Synopsis

The kinetics of oxidation of triphenyl derivatives of group V elements Ph3M (M = P, As Sb) by potassium peroxodisulfate have been investigated spectrophotometrically in 60% acetonitrile-40% water (v/v) mixture. The reaction follows second-order kinetics, first order in each reactant. Changes in the [H+] and ionic strength have negligible effect on the reaction rate. Addition of acrylonitrile fails to inhibit the rate. The results indicate a rate-determining nucleophilic displacement of the Ph3M molecule on the peroxide linkage. The relative rate order has been found to be Ph3P > PhsSb > Ph3As. This can be attributed to two conflicting trends.

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