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Kinetics and mechanism of (salen)Mn III ‐catalysed oxidation of organic sulfides with sodium hypochlorite
Author(s) -
Chellamani Arunachalam,
Harikengaram Sivalingam
Publication year - 2003
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.620
Subject(s) - chemistry , thioanisole , substituent , medicinal chemistry , manganese , acetonitrile , reaction rate constant , steric effects , sulfide , alkoxy group , alkyl , kinetics , solvent , reaction mechanism , hypochlorite , inorganic chemistry , catalysis , organic chemistry , physics , quantum mechanics
The oxidation of organic sulfides with several substituted oxo(salen)manganese(V) complexes was investigated in 90% acetonitrile–10% water and the reaction is second‐order overall, first‐order each in sulfide and complex. Electron‐releasing substituents in sulfides and electron‐withdrawing substituents in oxo(salen)manganese(V) complexes accelerate the rate of oxidation. The second‐order rate constants for the oxidation of p ‐substituted phenyl methyl sulfides follow a linear Hammett relationship with ρ = −1.85. However, correlation between log k 2 and 2σ is excellent with ρ = 0.48 for the oxidation of thioanisole by substituted oxomanganese(V) complexes. The rate of oxidation of alkyl phenyl sulfides and dialkyl sulfides with oxo complexes was also examined and the reactions show a moderate steric effect. Substituent, acid and solvent effect studies reveal the operation of an S N 2 mechanism. Copyright © 2003 John Wiley & Sons, Ltd.