Please use this identifier to cite or link to this item: http://nopr.niscair.res.in/handle/123456789/24719
Title: Kinetics and mechanism of (salen)MnIII catalyzed oxidation of methyl phenyl sulfides with sodium metaperiodate
Authors: Chellamani, Arunachalam
Subramanian, Ramasamy
Keywords: Kinetics;Reaction mechanisms;Organic sulfides;Sodium metaperiodate;Manganese;Salen
Issue Date: 12-Dec-2013
Abstract: The kinetics of (salen)MnIII complexes-catalyzed oxidation of phenyl methyl sulfides with periodate in 90% acetonitrile-10% water (v/v) mixture at 20 °C has been studied spectrophotometrically. The oxidation follows an overall second order kinetics, first order each in sulfide and oxo(salen)manganese(V) complex. Electron-releasing substituents in the phenyl ring accelerate the rate, whereas electron-withdrawing substituents produce the opposite effect. The log k2 values show better correlation with ( = –1.84 ± 0.06, r = 0.998) than with +/( = –0.976 ± 0.08, r = 0.979). Electron-releasing substituents at the 5,5'-positions of the salen ligand decrease the rate while the electron-withdrawing substituents enhance the rate of oxidation. Substituent, acid and solvent effect studies reveal an SN2 mechanism for the oxidation of aryl methyl sulfides with periodate catalyzed by (salen)MnIII complexes.
Page(s): 1584-1590
URI: http://hdl.handle.net/123456789/24719
ISSN: 0975-0975(Online); 0376-4710(Print)
Appears in Collections:IJC-A Vol.52A(12) [December 2013]

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