Sulfur atom-directed metal–ligand synergistic catalysis in zirconium/hafnium-oxo clusters for highly efficient amine oxidation

The performance applications (e.g., photocatalysis) of zirconium (Zr) and hafnium (Hf) based complexes are greatly hindered by the limited development of their structures and the relatively inert metal reactivity. In this work, we constructed two ultrastable Zr/Hf-based clusters (Zr9-TC4A and Hf9-TC4A) using hydrophobic 4-tert-butylthiacalix[4]arene (H4TC4A) ligands, in which unsaturated coordinated sulfur (S) atoms on the TC4A4- ligand can generate strong metal-ligand synergy with nearby active metal Zr/Hf sites. As a result, these two functionalized H4TC4A ligands modified Zr/Hf-oxo clusters, as catalysts for the amine oxidation reaction, exhibited excellent catalytic activity, achieving very high substrate conversion (>99%) and product selectivity (>90%). Combining comparative experiments and theoretical calculations, we found that these Zr/Hf-based cluster catalysts accomplish efficient amine oxidation reactions through synergistic effect between metals and ligands: (i) the photocatalytic benzylamine (BA) oxidation reaction was achieved by the synergistic effect of the dual active sites, in which, the naked S sites on the TC4A4- ligand oxidize the BA by photogenerated hole and oxygen molecules are reduced by photogenerated electrons on the metal active sites; (ii) in the aniline oxidation reaction, aniline was adsorbed by the bare S sites on ligands to be closer to metal active sites and then oxidized by the oxygen-containing radicals activated by the metal sites, thus completing the catalytic reaction under the synergistic catalytic effect of the proximity metal-ligand. In this work, the Zr/Hf-based complexes applied in the oxidation of organic amines have been realized using active S atom-directed metal-ligand synergistic catalysis and have demonstrated very high reactivity.