A hexagonal Ni6 cluster protected by 2-phenylethanethiol for catalytic conversion of toluene to benzaldehyde

Abstract

We have synthesized single crystals of a 2-phenylethanethiol-protected Ni₆ nanocluster, namely Ni₆(C₈H₉S)₁₂, which shows a hexagonal metallic core structure and reasonable stability. Interestingly this cluster is found to be an excellent candidate for the catalytic oxidation of toluene to benzaldehyde, with 100% conversion and 91% selectivity, showing application potential as an aromatic aldehyde in industry. Using DFT calculations, we rationalize the catalytic reaction mechanism for the conversion of toluene to benzaldehyde, and demonstrate that the presence of H₂O₂ initiates the Ni₆ cluster via a highly exothermic step to form a Ni₆O* intermediate which then results in active sites for the oxidation of toluene. What is interesting is that the likely steric geometry matching of the six-ring Ni₆ core, a dozen phenylethanethiol ligands and the aromatic reactant toluene could attain a synergistic effect to facilitate the production of benzaldehyde free of catalyst support.