4365-63-3Relevant articles and documents
Competitive behavior of nitrogen based axial ligands in the oxovanadium(IV)-salen catalyzed sulfoxidation of phenylmercaptoacetic acid
Kavitha, C.,Subramaniam, P.
, (2020/08/10)
The sulfoxidation of twelve phenylmercaptoacetic acids (PMAA) by H2O2 catalyzed by three oxovanadium(IV)-salen complexes, having varied substituents on PMAA and salen with regard to their position, size and inductive effect, has been performed spectrophotometrically in 100percent acetonitrile medium. Three nitrogen bases (NB), pyridine (Py), imidazole (ImH) and 1-methylimidazole (MeIm), were used as axial ligands. It has been found that the rate of sulfoxidation is not only tuned by the substituents on PMAA and salen, but it is also varied by the addition of nitrogen bases. The observed order of retardation found among the different nitrogen bases is ImH > MeIm > Py. The rate of reaction decreases with the increase in concentration of the NB axial ligands. The strongly binding ImH shows the least reactivity. Hydroperoxovanadium(V)-salen has been proposed as the sole active oxidizing species. A detailed mechanistic study reveals that the low rate constant values in the presence of the nitrogen base is due to the existence of competition of NB with H2O2 and PMAA during the formation of active species and the coordination of PMAA with active species, respectively. Both electron donating and electron withdrawing substituents on PMAA retard the sulfoxidation rate significantly. The Hammett correlation between the rate constants and substituent constants shows a non-linear concave downward curve which is explained by the existence of two different rate determining steps within the same mechanism; coordination of PMAA with the active species for electron withdrawing substituents and transfer of oxygen to PMAA for electron donating substituents. All the experimental observations are explained by proposing a suitable mechanism.
Modulation of catalytic activity by ligand oxides in the sulfoxidation of phenylmercaptoacetic acids by oxo(salen)chromium(V) complexes
Subramaniam,Anbarasan,Sugirtha Devi,Ramdass
, p. 14 - 22 (2016/09/07)
Mechanism of sulfoxidation of eleven para-substituted phenyl mercaptoacetic acids (PMAAs) by three oxo(salen)chromium(V)+PF6?complexes in the presence of different ligand oxides (LOs) such as triphenylphosphine oxide, pyridine N-oxide and 4-picoline N-oxide have been studied spectrophotometrically in 100% acetonitrile medium. Spectral and kinetic profiles establish the formation of adduct, O[dbnd]Cr(V)(salen)+-LO as the reactive intermediate in the catalytic cycle. The rate of sulfoxidation is found to be enhanced significantly by the addition of LOs and introduction of substituent in PMAA and salen complex. Both electron releasing and electron withdrawing substituents in the substrate and oxidant facilitate the rate of sulfoxidation. Correlation with Hammett constants yields a non-linear concave upward curve. Based on the experimental results and substituent effects two different mechanisms, a direct oxygen atom transfer (DOT) for PMAAs with electron withdrawing substituents and a single electron transfer for PMAAs with electron donating substituents have been postulated.
Spectral and mechanistic investigation of Oxidative Decarboxylation of Phenylsulfinylacetic Acid by Cr(VI)
Subramaniam, Perumal,Selvi, Natesan Thamil,Devi, Soundarapandian Sugirtha
, p. 17 - 24 (2014/03/21)
The oxidative decarboxylation of phenylsulfinylacetic acid (PSAA) by Cr(VI) in 20% acetonitrile - 80% water (v/v) medium follows overall second order kinetics, first order each with respect to [PSAA] and [Cr(VI)] at constant [H+] and ionic strength. The reaction is acid catalysed, the order with respect to [H+] is unity and the active oxidizing species is found to be HCrO3+. The reaction mechanism involves the rate determining nucleophilic attack of sulfur atom of PSAA on chromium of HCrO3+ forming a sulfonium ion intermediate. The intermediate then undergoes a,β-cleavage leading to the liberation of CO2. The product of the reaction is found to be methyl phenyl sulfone. The operation of substituent effect shows that PSAA containing electron-releasing groups in the meta- and para-positions accelerate the reaction rate while electron withdrawing groups retard the rate. An excellent correlation is found to exist between log k2 and Hammett s constants with a negative value of reaction constant. The p value decreases with increase in temperature evidencing the high reactivity and low selectivity in the case of substituted PSAAs.