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Ligand-to-metal charge transfer of a pyridine surface complex on TiO2 for selective dehydrogenative cross-coupling
Shimpei Naniwa1, Shinichiro Hishitani1, Akira Yamamoto2
1Department of Interdisciplinary Environment, Graduate School of Human and Environmental Studies, Kyoto University, Yoshida Nihonmatsu-cho, Sakyo-ku, Kyoto 606-8501, Japan. yoshida.hisao.2a@kyoto-u.ac.jp.
Abstract:
Dehydrogenative cross-coupling (DCC) between pyridine and benzene proceeded selectively using a TiO2 photocatalyst under visible light irradiation at optimized concentrations of the substrates. Visible light induces ligand-to-metal charge transfer (LMCT) between pyridine and a TiO2 surface to give a pyridine radical cation, which produces a pyridyl radical by its deprotonation or oxidation of another pyridine molecule. The pyridyl radical attacks a benzene ring to form an sp2C-sp2C bond and a hydrogen atom is subsequently removed to complete DCC. Selective excitation of the pyridine LMCT complex in the presence of an excess amount of benzene would be the key for higher selectivity.
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