Multi-Enzyme Mimicry by Dinuclear Transition Metal Complexes with Oxime Ligand

Year 2025, Volume: 11 Issue: 4, 369 - 381, 31.12.2025

Gamze Özdemir , Bülent Dede

https://doi.org/10.28979/jarnas.1769716

Abstract

This study focuses on the comparative evaluation of the catalase-, catecholase-, and
phenoxazinone synthase-like activities of six dinuclear oxime-based metal(II) complexes containing
Mn(II), Fe(II), Co(II), Ni(II), Cu(II), and Zn(II) ions. The enzymatic models were investigated
spectrophotometrically under ambient conditions using hydrogen peroxide, 3,5-di-tert-butylcatechol
(3,5-DTBC), and 2-aminophenol as substrates, respectively. Among all the complexes, the Cu(II)
complex exhibited superior catalytic efficiency in all three models, demonstrating the highest
molecular oxygen (O2) release in the catalase assay and the fastest oxidation rates in both catecholase
and phenoxazinone synthase reactions. Mn(II) and Co(II) complexes followed with moderately high
activities, while Ni(II) and Zn(II) derivatives showed significantly lower catalytic responses due to
their limited redox flexibility. The variation in rate constants and oxygen evolution profiles
highlighted distinct structure–activity relationships in each case. These findings reveal that while no
single complex was universally dominant across all assays, Cu(II)-based systems displayed the most
consistent and effective biomimetic behavior overall. This work highlights the versatility of oximebridged
dinuclear complexes as functional mimics of oxidoreductase enzymes and their potential
applications in the field of bioinspired catalysis.

Keywords

Dinuclear metal complexes , biomimetic oxidation , catalase , catecholase , phenoxazinone synthase

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