Preparation and Catalytic Performances of a Molecularly Imprinted Ru‐Complex Catalyst with an NH 2 Binding Site on a SiO 2 Surface

A catalyst surface with an active metal site, a shape‐selective reaction space, and an NH 2 binding site for o ‐fluorobenzophenone was designed and prepared by the molecular imprinting of a supported metal complex on a SiO 2 surface. A ligand of a SiO 2 ‐supported Ru complex that has a similar shape to the product of o ‐fluorobenzophenone hydrogenation was used as a template. An NH 2 binding site for o ‐fluorobenzophenone was spatially arranged on the wall of a molecularly imprinted cavity with a similar shape to the template. The structures of the SiO 2 ‐supported and molecularly imprinted Ru catalysts were characterized in a step‐by‐step manner by means of solid‐state magic angle spinning (MAS) NMR, XPS, UV/Vis, N 2 adsorption, XRF, and Ru K‐edge EXAFS. The molecularly imprinted Ru catalyst exhibited excellent shape selectivity for the transfer hydrogenation of benzophenone derivatives. It was found that the NH 2 binding site on the wall of the molecularly imprinted cavity enhanced the adsorption of o ‐fluorobenzophenone, of which the reduction product was imprinted, whereas there was no positive effect in the case of o ‐methylbenzophenone, which cannot interact with the NH 2 binding site through hydrogen bonding.