Facile Synthesis of β-Tetracyano Vanadyl Porphyrin from Its Tetrabromo Analogue and Its Excellent Catalytic Activity for Bromination and Epoxidation Reactions

Abstract

Complex 2,3,12,13-tetracyano-5,10,15,20-tetraphenylporphyrinatooxidovanadium(IV) {[V^IVOTPP(CN)₄], <b>2</b>} has been prepared by nucleophilic substitution of β-bromo groups of the corresponding 2,3,12,13-tetrabromo-5,10,15,20-tetraphenylporphyrinatooxidovanadium(IV) {[V^IVOTPP(Br)₄], <b>1</b>} using CuCN in quinoline. Both complexes show biomimetic catalytic activity similar to enzyme haloperoxidases and efficiently brominate various phenol derivatives in the presence of KBr, H₂O₂, and HClO₄ in the aqueous medium. Between these two complexes, <b>2</b> exhibits excellent catalytic activity with high turnover frequency (35.5-43.3 s^-1) due to the strong electron-withdrawing nature of the cyano groups attached at β-positions and its moderate nonplanar structure as compared to <b>1</b> (TOF = 22.1-27.4 s^-1). Notably, this is the highest turnover frequency value observed for any porphyrin system. The selective epoxidation of various terminal alkenes using complex <b>2</b> has also been carried out, and the results are good, specifying the importance of electron-withdrawing cyano groups. Catalysts <b>1</b> and <b>2</b> are recyclable, and the catalytic activity proceeds through the corresponding [V^VO(<i>OH</i>)TPP(Br)₄] and [V^VO(<i>OH</i>)TPP(CN)₄] intermediates, respectively.