Development of Titanium Dioxide-Supported Pd Catalysts for Ligand-Free Suzuki-Miyaura Coupling of Aryl Chlorides

被引:18
作者
Yamada, Tsuyoshi [1 ]
Masuda, Hayato [1 ]
Park, Kwihwan [1 ]
Tachikawa, Takumu [1 ]
Ito, Naoya [1 ]
Ichikawa, Tomohiro [1 ]
Yoshimura, Masatoshi [2 ]
Takagi, Yukio [2 ]
Sawama, Yoshinari [1 ]
Ohya, Yutaka [3 ]
Sajiki, Hironao [1 ]
机构
[1] Gifu Pharmaceut Univ, Lab Organ Chem, 1-25-4 Daigaku Nishi, Gifu 5011196, Japan
[2] NE Chemcat Corp, Catalysts Dev Ctr, 678 Ipponmatsu, Numazu 4100314, Japan
[3] Gifu Univ, Dept Chem & Biomol Sci, 1-1 Yanagido, Gifu 5011193, Japan
基金
日本学术振兴会;
关键词
Suzuki-Miyaura reaction; palladium; heterogeneous catalyst; titanium oxide; anatase titania; aromatic chloride; HETEROGENEOUS PALLADIUM CATALYST; MESOPOROUS SILICA; HIGHLY EFFICIENT; NANOCOMPOSITE CATALYSTS; HYDROGEN GENERATION; BOND FORMATION; CARBON-CARBON; SOLVENT-FREE; NANOPARTICLES; REDUCTION;
D O I
10.3390/catal9050461
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The catalyst activities of various heterogeneous palladium catalysts supported by anatase-, rutile- and brookite-type titanium oxide for ligand-free Suzuki-Miyaura cross-coupling reactions of aryl chlorides were evaluated. Palladium acetate [Pd(OAc)(2)], supported on anatase-type titanium oxide (TiO2) via acetonitrile solution impregnation process without reduction [Pd/TiO2 (anatase-type)], demonstrated the highest catalyst activity in comparison to those of other titanium oxide (rutile- or brookite-type) supported Pd(OAc)(2) without reduction and reduced Pd/TiO2 (anatase-type) [Pd(red)/TiO2 (anatase-type)]. Various aryl chloride and bromide derivatives were smoothly coupled with arylboronic acids including heteroarylboronic acids in the presence of 5-10 mol% Pd/TiO2 (anatase-type) without the addition of any ligands. Although the fresh Pd/TiO2 (anatase-type) catalyst was surprisingly comprised of ca. 1:2 mixture of palladium(II) and palladium(0) species according to X-ray photoelectron spectroscopy (XPS), in spite of no reduction process, significant further increment of palladium(0) species was observed during the Suzuki-Miyaura coupling reaction, and Pd/TiO2 (anatase-type) was converted into a catalyst, which contained palladium(0) species as the main component [ca. 1:5 mixture of palladium(II) and palladium(0) species]. Therefore, the reduction via the electron donation process to the palladium(II) species may have occurred during the reaction on anatase-type titanium oxide.
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页数:14
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