Molybdenum (VI) Complexes Containing Pyridylimine Ligands: Effect of the Imine Nitrogen Substituent in the Epoxidation Reaction

A series of pyridylimine ligands with variations of the substituent at the imine nitrogen were synthesized and coordinated to the [MoCl2O2] core. The novel molecular structures of the complexes were fully characterized by 1H and 13C NMR, FT‐IR, ESI, EA, and X‐ray crystallography, and their catalytic activity was studied for the epoxidation of alkenes using tert‐butyl hydroperoxide (TBHP) as the oxidant. The new complexes showed excellent catalytic activity and fine selectivity in the epoxidation reaction compared with similar homogeneous molybdenum complexes. The results demonstrated that there is a significant change in the catalytic performance, depending on the alkyl arm on the structure of the pyridilimine ligand. The catalytic results indicated that complex [MoCl2O2(L)] (L: N‐(2‐Pyridinylmethylene)‐1‐tert‐butylimine) C5 is the best catalytic precursor in the epoxidation of cyclohexene (TON: 92920 and TOF: 30974 h−1). Dioxomolybdenum (VI) complexes with the general formula [MoCl2O2(pyridilimine)] were applied as homogeneous catalysts for the epoxidation of olefins. The new compounds showed high catalytic activity. The performance of the complexes in the reaction can be attributed to the substituent at the imine fragment.