A novel µ-carbido hetero-binuclear iron-ruthenium heteroleptic complex on macrocyclic platforms with efficient oxidative activity

Abstract

Bimetallic µ-bridged complexes supported by macrocycles are worth addressing due to their excellent stability, rich redox chemistry and suitability in catalysis. This paper for the first-time reports on the synthesis and redox properties of an unexplored heterometallic μ-carbido-dimer derivative bearing iron-porphyrin and ruthenium-phthalocyanine parts and a FeIV = C = RuIV unit. The compound is identified by UV–visible, IR, EPR, MALDI TOF, electrochemistry techniques and DFT calculations. The redox activity of the compound toward H2O2, tBuOOH is examined. The results indicate that under oxidation conditions in dichloromethane, benzene and acetonitrile, the initial complex evolves rapidly via oxidation steps forming intermediates which are competent in β-carotene and methylene blue oxidation at room temperature. The site oxidation accessibility of the initial compound and the nature of high-charged intermediate species are established to depend on the solvent polarity and axial ligands. The findings contribute to a deeper understanding of the significant role of reaction conditions as well as the mixed macrocyclic ligand environment and metal nature in controlling the oxidizing capability and thus can aid the development of new more active and durable catalysts.