Importance of ground state stabilization in the oxovanadium(IV)-salophen mediated reactions of phenylsulfinylacetic acids by hydrogen peroxide – Non-linear Hammett correlation

A systematic study on the oxidative decarboxylation of a series of phenylsulfinylacetic acids (PSAA) by hydrogen peroxide with four oxovanadium(IV)-salophen catalysts in 100% acetonitrile medium is presented. The hydroperoxovanadium(V)-salophen generated from the reaction mixture is identified as the bonafide active oxidizing species. Introduction of electron donating groups (EDG) in the oxovanadium(IV)-salophen catalyst and electron withdrawing groups (EWG) in PSAA enhances the reactivity, whereas EWG in the catalyst and EDG in PSAA have a retarding effect on the reaction. A Hammett correlation displays a non-linear downward curvature, which consists of two intersecting straight lines and the ρ value shifts from small positive to moderately high as the substituents change from EWG to EDG. The importance of the ground state stabilization of PSAA is inferred from a linear Yukawa–Tsuno plot. Based on the observed substituent effects and the spectral changes, a mechanism involving electrophilic attack of PSAA on the nucleophilic peroxo oxygen atom of the vanadium complex in the rate determining step followed by oxygen atom transfer is proposed.

Hydroperoxovanadium(V)-salophen is identified as the oxidizing species. Electron donating groups in the complex and withdrawing groups in phenylsulfinylacetic acid enhance the reaction. Ground state stabilization is inferred from a non-linear Hammett correlation and linear Yukawa–Tsuno plot. The mechanism proposed involves electrophilic attack of phenylsulfinylacetic acid on the nucleophilic peroxo oxygen atom of the vanadium complex.Figure optionsDownload as PowerPoint slide