Highly Efficient β‐Functionalized Oxidomolybdenum(V) Corroles for Catalytic Oxidative Bromination of Phenols at Room Temperature

Abstract

AbstractTwo new β‐functionalized oxidomolybdenum(V) corroles, oxido[3‐formyl‐5,10,15‐triphenylcorrolato]molybdenum(V) (Mo‐1) and oxido[3‐dicyanovinyl‐5,10,15‐triphenylcorrolato]molybdenum(V) (Mo‐2) were synthesized and characterized by various spectroscopic techniques and electrochemical studies. Mo‐2 manifests splitted B bands due to x and y polarizations and highly red shifted longest B and Q bands due to the electron‐deficient nature of the dicyanovinyl group. EPR data showed that these complexes exhibit an axial compression with dxy1 configuration. DFT studies revealed that HOMO and LUMO orbitals are stabilized in Mo‐2 relative to Mo‐1. Mo‐1 exhibits two successive reversible reductions and two oxidation potentials in cyclic voltammetry. Surprisingly, Mo‐2 exhibits three successive reversible reductions and two oxidations; the one extra reduction could possibly be due to the reduction of the dicyanovinyl moiety. The catalytic activities of Mo‐1 and Mo‐2 for the oxidative bromination of various phenols using H2O2‐KBr‐HClO4 mixture in water have been explored and exhibited excellent activity at a very low catalyst loading of 0.0030 and 0.0028 mol%, respectively. Both synthesized β‐functionalized Mo(V) corroles manifest much higher conversion and TOF (59801–71174 h−1) for oxidative bromination of phenols relative to earlier reported meso‐functionalized Mo(V) corroles (20781–61646 h−1). Hence, Mo‐1 and Mo‐2 mimic vanadium bromoperoxidase (VBPO) and act as functional models for these catalytic applications. These catalysts were reused upto 3 cycles and showed conversion rate upto 82 % indicating their excellent thermal and chemical stabilities.