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Published on: February 6, 2020
Head-to-Tail Oligomerization by Silylene-Tethered Sonogashira Coupling on Ag(111)
Kewei Sun1, Keisuke Sagisaka1, Lifen Peng2,3
1Research Center for Advanced Measurement and Characterization, National Institute for Materials Science, Sengen 1-2-1, Tsukuba, Ibaraki, 305-0047, Japan.
Abstract:
On-surface synthesis is a powerful method for the fabrication of π-conjugated nanomaterials. Herein, we demonstrate chemoselective Sonogashira coupling between (trimethylsilyl)ethynyl and chlorophenyl groups in silylethynyl- and chloro-substituted partially fluorinated phenylene ethynylenes (SiCPFPEs) on Ag(111). The desilylative Sonogashira coupling occurred with high chemoselectivity up to 75 %, while the competing Ullmann and desilylative Glaser homocoupling reactions were suppressed. A combination of bond-resolved scanning tunneling microscopy/atomic force microscopy (STM/AFM) and DFT calculations revealed that the oligomers were obtained by the formation of intermolecular silylene tethers (-Me2 Si-) through CH3 -Si bond activation at 130 °C and subsequent elimination of the tethers at an elevated temperature of 200 °C.
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