Roles of basicity and steric crowding of anionic coligands in catechol oxidase-like activity of Cu(ii)-Mn(ii) complexes.

Five new heterometallic Cu(ii)-Mn(ii) discrete trinuclear complexes, [(CuL)2Mn(CH3COO)2] (1), [(CuL)2Mn(NO3)2] (2), [(CuL)2Mn(C6H5COO)(H2O)]Cl (3), [(CuL)2Mn((p-OH)C6H5COO)(H2O)]ClO4 (4) and [(CuL)2Mn(HCOO)(H2O)]ClO4 (5), have been synthesized using a metalloligand, CuL derived from an N2O2 donor Schiff base, H2L (N,N'-bis(α-methylsalicylidene)-1,3-propanediamine). Single-crystal structural analyses reveal that all five complexes have a common [(CuL)2Mn] core, where two terminal metalloligands, CuL, are connected to the central metal ion, Mn(ii), via double phenoxido bridges. Among the complexes, 1 and 2 possess linear structures where the terminal Cu(ii) atoms are bridged to the central Mn(ii) atoms by acetate and nitrate ions, respectively along with the double phenoxido bridges, whereas 3, 4 and 5 have bent structures in which the respective anionic coligands, benzoate, p-hydroxybenzoate and formate ions are coordinated only to central Mn(ii) in monodentate fashion along with a water molecule that completes its hexa-coordinated geometry. Among the complexes, 1, 3, 4 and 5 show quite high bio-mimicking catecholase-like activity for the aerial oxidation of 3,5-di-tert-butylcatechol with turnover numbers (Kcat) of 139 h-1, 439 h-1, 348 h-1 and 730 h-1, respectively, whereas complex 2 is practically inactive towards this reaction. The presence of the coordinated water molecule to Mn(ii) in the bent complexes, 3-5, appears to be responsible for their high catalytic activity and the difference in their activity may be attributed to steric crowding due to the anionic coligand, whereas the inactivity of 2 seems to be associated with the low basicity of the nitrate ion. The temperature-dependent dc molar magnetic susceptibility measurements reveal that complexes 1-5 are antiferromagnetically coupled with the exchange coupling constants (J) = -8.54 cm-1, -11.50 cm-1, -19.83 cm-1, -10.65 cm-1 and -10.27 cm-1 for 1, 2, 3, 4 and 5 respectively as is expected from the Cu-O-Mn bridging angles.