Hybrid organic-inorganic Cu(II) iminoisonicotine@TiO2@Fe3O4 heterostructure as efficient catalyst for cross-couplings

Two novel mononuclear copper (II) complex catalysts were synthesized from a new tridentate iminoisonicotine ligand (HL) by coordination with Cu(II) ion, with (CuL@TiO₂@Fe₃O₄) and without (CuL) immobilization on TiO₂-coated nanoparticles of Fe₃O₄. The ester moiety on the back of the ligand was utilized for immobilization on nanoparticles of Fe₃O₄. Both ligand and CuL complex were fully characterized by using alternative spectral techniques (nuclear magnetic resonance, infrared, ultraviolet-visible and mass spectroscopy, and elemental analyses). Different analytical techniques were used to identify the structural feature and morphology of the immobilized copper catalyst (CuL@TiO₂@Fe₃O₄) shell-shell-core system. The structural analysis revealed that the catalyst system is composed of both agglomerated nanospheres and deformed nanorods. Both copper catalysts, immobilized CuL@TiO₂@Fe₃O₄ and un-immobilized CuL were studied in heterogeneous and homogeneous catalysis, respectively, for Suzuki-Miyaura (C–C) and Buchwald-Hartwig (C–N) cross-coupling reactions of various heteroaryl halides. Both catalysts showed good catalytic potential under the controlled optimal reaction conditions. In contrast to the homogeneous catalyst (CuL), the heterogeneous catalyst (CuL@TiO₂@Fe₃O₄) showed slightly better catalytic performance. The characteristic obtains supported the catalytic potential of the current samples. Reusability/recycling of both catalysts was also investigated in C–C cross-coupling reactions. It was found that the homogeneous catalyst (CuL) could be only recycled up to three times, whereas the heterogeneous one (CuL@TiO₂@Fe₃O₄) could be reused up to seven times with good efficiency.