TY - JOUR
T1 - Preparation and catalytic performances of a molecularly imprinted RU-complex catalyst with an NH 2 binding site on a SiO 2 surface
AU - Yang, Yong
AU - Weng, Zhihuan
AU - Muratsugu, Satoshi
AU - Ishiguro, Nozomu
AU - Ohkoshi, Shin Ichi
AU - Tada, Mizuki
PY - 2012/1/23
Y1 - 2012/1/23
N2 - 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. Tailoring a pocket: A molecularly imprinted Ru-complex catalyst with an NH 2 binding site for o-fluorobenzophenone has been successfully designed and prepared on a SiO 2 surface for shape-selective transfer hydrogenation (see scheme).
AB - 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. Tailoring a pocket: A molecularly imprinted Ru-complex catalyst with an NH 2 binding site for o-fluorobenzophenone has been successfully designed and prepared on a SiO 2 surface for shape-selective transfer hydrogenation (see scheme).
KW - hydrogenation
KW - imprinting
KW - molecular recognition
KW - ruthenium
KW - supported catalysts
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U2 - 10.1002/chem.201100529
DO - 10.1002/chem.201100529
M3 - Article
AN - SCOPUS:84862908475
SN - 0947-6539
VL - 18
SP - 1142
EP - 1153
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
IS - 4
ER -