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- Title
Surface‐Dependent Chemoselectivity in C−C Coupling Reactions.
- Authors
Chen, Zhi; Lin, Tao; Zhang, Liding; Zhang, Lei; Xiang, Bingxi; Xu, Hu; Klappenberger, Florian; Barth, Johannes V.; Klyatskaya, Svetlana; Ruben, Mario
- Abstract
Surface‐confined covalent coupling reactions of the linear compound 4‐(but‐3‐en‐1‐ynyl)‐4′‐ethynyl‐1,1′‐biphenyl (1), which contains one alkyne and one enyne group on opposing ends, have been investigated using scanning tunneling microscopy (STM) and density functional theory (DFT) calculations. The reactions show a surface‐dependent chemoselectivity: on Au(111), compound 1 preferentially yields cyclotrimerization products, while on Cu(111), a selective coupling between the enyne and alkyne groups is observed. Linear, V‐shaped string formations combined with Y‐shaped bifurcation motifs result in a random reticulation on the entire surface. DFT calculations show that the C−H⋅⋅⋅πδ− transition state of the reaction between the deprotonated alkyne group and a nearby H‐donor of the alkene group plays a key role in the mechanism and high chemoselectivity. This study highlights a concept that opens new avenues to the surface‐confined synthesis of covalent carbon‐based sp–sp2 polymers.
- Subjects
CHEMOSELECTIVITY; CARBON-carbon bonds; COUPLING reactions (Chemistry); DENSITY functional theory; COVALENT bonds
- Publication
Angewandte Chemie, 2019, Vol 131, Issue 25, p8444
- ISSN
0044-8249
- Publication type
Article
- DOI
10.1002/ange.201900636