期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 140, 期 24, 页码 7526-7532出版社
AMER CHEMICAL SOC
DOI: 10.1021/jacs.8b01658
关键词
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资金
- Deutsche Forschungsgemeinschaft [GO 1812/2-1, HI 655/18-1]
- CRC [1083]
- Cluster of Excellence [EXC 315]
- GRK (Research Training Group) [2204]
- Laboratory of Materials Research (LaMa) of JLU
- LOEWE program of excellence of the Federal State of Hessen (project initiative STORE-E)
- Alexander von Humboldt Foundation
Aromatic C-H bond activation has attracted much attention due to its versatile applications in the synthesis of aryl-containing chemicals. The major challenge lies in the minimization of the activation barrier and maximization of the regioselectivity. Here, we report the highly selective activation of the central aromatic C-H bond in meta-aryne species anchored to a copper surface, which catalyzes the C-H bond dissociation. Two prototype molecules, i.e., 4',6'-dibromo-meta-terphenyl and 3',5'-dibromo-ortho-terphenyl, have been employed to perform C-C coupling reactions on Cu(III). The chemical structures of the resulting products have been clarified by a combination of scanning tunneling microscopy and noncontact atomic force microscopy. Both methods demonstrate a remarkable weakening of the targeted C-H bond. Density functional theory calculations reveal that this efficient C-H activation stems from the extraordinary chemisorption of the meta-aryne on the Cu(III) surface, resulting in the close proximity of the targeted C-H group to the Cu(III) surface and the absence of planarity of the phenyl ring. These effects lead to a lowering of the C-H dissociation barrier from 1.80 to 1.12 eV, in agreement with the experimental data.
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