Solvent dependent ligand transformation in a dinuclear copper(II) complex of a compartmental Mannich-base ligand: synthesis, characterization, bio-relevant catalytic promiscuity and magnetic study

摘要

An "end-off" pentadentate compartmental ligand HL has been synthesized by Mannich base condensation using p-cresol and 2-benzyl amino ethanol and structurally characterized. A dinuclear copper(II) complex, namely [Cu-2(L)(mu-OH)(H2O)(ClO4)(2)], has been prepared by treating HL with Cu(ClO4)(2)center dot 6H(2)O in methanolic solution with the aim of investigating its catalytic promiscuity. Single crystal structural analysis reveals that the Cu-Cu separation is 2.9 angstrom. Catecholase activity of the complex has been investigated in anhydrous DMSO as well as in a DMSO-water mixture with progressively increasing the quantity of water up to a 1 : 1 volume ratio in order to assess the bio compatibility of the catalyst using 3,5-DTBC as a model substrate. In anhydrous DMSO the catalytic activity reaches its peak and decreases with increasing water concentration, a feature most likely due to insolubility of 3,5-DTBQ, the product formed in the catalysis, in water. The complex also shows excellent phosphatase-like activity by exploiting the Lewis acidity, the necessary requirement for that activity, under different pH. Thorough investigation reveals that no activity is observed at pH 6 but the activity increases with increasing pH and attains a maximum at pH 9. A variable temperature magnetic study shows that the two Cu centers are antiferromagnetically coupled at low temperature with a J value of -78.63 + 1.30 cm(-1). In acetonitrile medium the complex shows very exciting behavior. A new transformed ligand is generated that has been assigned as a Schiff-base ligand, 2,6-bis-[(2-hydroxy-ethylimino)-methyl]-4-methylphenol. The genesis of the new ligand is a consequence of dealkylation from HL followed by oxidation. This oxidation is counterbalanced by reduction of Cu(II) to Cu(I) as is evidenced from isolation of [Cu(MeCN)(4)](ClO4) from the mixture followed by X-ray structural characterization of the species.