Fabrication and catalytic properties of ordered cyclopalladated diimine monolayer : investigation on catalytic mechanism

Abstract

“Channel-like” self-assembled monolayers having aliphatic and aromatic diimines (denoted as Si@1DIS, Si@2DIS and Si@3DIS) immobilized on substrates and their palladacycle monolayers (Si@1DIS-Pd, Si@2DIS-Pd and Si@3DIS-Pd) were prepared and characterized. Their catalytic performances were investigated using the Suzuki coupling reaction as a model. Si@3DIS-Pd showed the highest catalytic activity in water without ligands, and better recyclability than that of Si@2DIS-Pd and Si@1DIS-Pd. The reason was the carbon in the aliphatic diimine of Si@2DIS-Pd and Si@1DIS-Pd was easily hydrolyzed because of the active hydrogen of α-C, resulting in poor recyclability. Control of the amount of catalyst could be achieved by modulating the diameter of the channel-like structure, which also affected the catalytic activity. The catalytic process and mechanism were investigated systematically and proposed based on the experimental results obtained by the water contact angle, ultraviolet spectroscopy, X-ray photoelectron spectroscopy, cyclic voltammetry and atomic force spectroscopy. Changes in the morphology of monolayer surfaces during the catalytic process with or without stirring presented a clear process from order to disorder, and indicated that the reaction was a heterogeneous catalytic process occurring on the surface of the catalyst monolayer.