| Article ID | Journal | Published Year | Pages | File Type |
|---|---|---|---|---|
| 1336334 | Polyhedron | 2016 | 10 Pages |
The mechanism of oxidative decarboxylation of phenylsulfinylacetic acids (PSAA) by oxo(salen)Cr(V)+ ion in the presence of ligand oxides has been studied spectrophotometrically in acetonitrile medium. Addition of ligand oxides (LO) causes a red shift in the λmax values of oxo(salen) complexes and an increase in absorbance with the concentration of LO along with a clear isobestic point. The reaction shows first-order dependence on oxo(salen)-chromium(V)+ ion and fractional-order dependence on PSAA and ligand oxide. Michaelis–Menten kinetics without kinetic saturation was observed for the reaction. The order of reactivity among the ligand oxides is picoline N-oxide > pyridine N-oxide > triphenylphosphine oxide. The low catalytic activity of TPPO was rationalized. Both electron-withdrawing and electron-donating substituents in the phenyl ring of PSAA facilitate the reaction rate. The Hammett plots are non-linear upward type with negative ρ value for electron-donating substituents, (ρ− = −0.740 to −4.10) and positive ρ value for electron-withdrawing substituents (ρ+ = +0.057 to +0.886). Non-linear Hammett plot is explained by two possible mechanistic scenarios, electrophilic and nucleophilic attack of oxo(salen)chromium(V)+-LO adduct on PSAA as the substituent in PSAA is changed from electron-donating to electron-withdrawing. The linearity in the log k vs. Eox plot confirms single-electron transfer (SET) mechanism for PSAAs with electron-donating substituents.
Graphical abstractOxidative decarboxylation of PSAAs by oxo(salen)chromium(V) complexes in the presence of ligand oxides proceeds through Michaelis–Menten kinetics without kinetic saturation. The order of reactivity among the three ligand oxides is PicNO > PyO > TPPO. The observed non-linearity in the Hammett plot is due to change in reaction mechanism.Figure optionsDownload full-size imageDownload as PowerPoint slide
