A rare flattened tetrahedral Mn(II) salen type complex: Synthesis, crystal structure, biomimetic catalysis and DFT study

摘要

A new flattened tetrahedral high spin Mn(II) complex (1) has been synthesized using N2O4 donor Schiff base ligand. Complex 1 was characterized by X-ray diffraction and various spectroscopic techniques. For further understanding of electronic structure of the complex, DFT calculations and electrochemical studies have been performed. This is a rare example of a flattened tetrahedral Mn(II) salen type Schiff base complex. High-spin d(5) configuration of the metal center provides no crystal-field stabilization energy to the system and that is the main reason behind the significant deviation of this salen-type ligand from planarity. Notably, the propylenic linker in the ligand provides adequate flexibility so that such an uncommon binding mode of the salen type Schiff base ligand becomes possible. Complex 1 exhibits excellent catalytic property towards oxidation of o-aminophenols in aerobic condition. Detailed kinetic investigations together with the mass spectrometry studies reveal several important information relating to biomimetic catalytic activity of the present complex.