Trans‐Dioxidomolybdenum(VI) Porphyrins and their Catalytic Activity Mimicking Oxidative Bromination

Abstract Synthesis of trans ‐dioxidomolybdenum(VI)‐ meso ‐tetraphenylporphyrin ( trans ‐[Mo VI O 2 (TPP)], 1 ) and trans ‐dioxidomolybdenum(VI)‐ meso ‐tetra( p ‐chlorophenyl)porphyrin ( trans ‐[Mo VI O 2 (TCPP)], 2 ) by reacting the corresponding free‐base porphyrins with Mo(CO) 6 in 1,2,4‐trichlorobenzene at 190 °C has been reported. These are the second examples in the literature where molybdenum‐porphyrins have trans ‐[Mo VI O 2 ] group, identified by single crystal X‐ray study. Both complexes have been utilized as functional model of haloperoxidases for the oxidative bromination of various phenol derivatives using KBr, H 2 O 2 and HClO 4 as green brominating reagents in aqueous medium. These complexes displayed very high TOF values (up to 16.2 s −1 for catalyst 2 ) representing excellent catalytic activity. To the best of our knowledge, this is the first report presenting trans ‐dioxidomolybdenum(VI) based porphyrin as haloperoxidases mimicking oxidative bromination of various phenol derivatives.