Synthesis of Ni(<scp>ii</scp>)–Mn(<scp>ii</scp>) complexes using a new mononuclear Ni(<scp>ii</scp>) complex of an unsymmetrical N₂O₃ donor ligand: structures, magnetic properties and catalytic oxidase activity

Abstract

A new Ni(ii) complex [NiL] (complex 1) of an asymmetrically di-condensed N₂O₃ donor Schiff base ligand, N-salicylidene-N'-3-methoxysalicylidene-1,3-propanediamine (H₂L), has been synthesized and utilized for the synthesis of three heterometallic complexes, [(NiL)₂Mn(NCS)₂(CH₃OH)₂]·CH₃OH (2) [(NiL)₂Mn(N(CN)₂)₂(CH₃OH)₂]·CH₃OH (3) and [(NiL)₂Mn₂(N₃)₂(μ_1,1-N₃)₂(CH₃OH)₂] (4). Single crystal X-ray diffraction analyses show that complexes 2 and 3 have linear trinuclear structures where two tridentate O₃ donor (NiL) units are coordinated to the central octahedral Mn(ii) centre, whereas complex 4 has a centrosymmetric tetranuclear structure where two binuclear (NiL)Mn units are linked via two phenoxido and two μ_1,1-N₃ bridges. Among the heterometallic complexes (2-4), only 4 is active towards the catalytic oxidation of 3,5-di-tert-butylcatechol to the corresponding quinone. The turnover number for the aerobic oxidation of 3,5-DTBC is 935 h^-1. ESI-mass spectra have been recorded to scrutinize the mechanistic pathway of this catalytic reaction. Variable temperature magnetic susceptibility measurements suggest that complexes 2-4 are antiferromagnetically coupled with coupling constants (J) of -4.84 and -5.23 cm^-1 for complexes 2 and 3, respectively and J₁ = -2.20 cm^-1, J₂ = 1.13 cm^-1 and J₃ = -1.12 cm^-1 for complex 4. DFT calculations have been used to rationalize the magnetic super-exchange in complexes 2-4, by computing the theoretical coupling constants and analyzing the spin density plots.