Study of interactive free-energy relationships on ruthenium(III) catalyzed oxidation of phenyl styryl ketone and its substituted analogues by V(V) in acid medium
✍ Scribed by S. R. Annapoorna; M. Prasad Rao; B. Sethuram
- Publisher
- John Wiley and Sons
- Year
- 2000
- Tongue
- English
- Weight
- 130 KB
- Volume
- 32
- Category
- Article
- ISSN
- 0538-8066
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✦ Synopsis
Kinetics of Ru(III) catalyzed oxidation of phenyl styryl ketone (PSK) and its substituted analogues by V(V) has been investigated in aqueous acetic acid-sulphuric acid medium in the temperature range 298-313 K. First-order dependence each on [V(V)], [PSK], and [Ru(III)] was observed. Inverse first-order dependence was observed for [V(IV)]. The rate decreased with the increase in dielectric constant (D) of the medium. The rates were enhanced by electron-donating substituents in both the phenyl rings and decreased by electron-withdrawing substituents. Linear Hammett's plots were obtained for various substituents in benzaldehyde moiety of PSK for a given substituent in acetophenone moiety and vice versa. The mechanism proposed envisages formation of Ru(IV) from V(V) ϩ Ru(III) reaction followed by the attack on C " O by Ru(IV). Applicability of interactive free-energy relationship has been tested. The cross-interaction constants q x and q y have been determined at different temperatures and possible interpretations discussed.