J. Am. Chem. Soc. 19, 144 (2022)

Desilylative Coupling Involving C(sp2)–Si Bond Cleavage on Metal Surfaces

Kang Ma¹, Tiantong Zhang¹, Ying Qin², Zhixin Hu³, Zhixiang Sun^3,*, You Han^1,*, Dongbing Zhao^2,* and Hong-Ying Gao^1,*

1 Department of Physics & Center for Joint Quantum Studies, Tianjin University, Tianjin 300350, China.

2 School of Chemical Engineering and Technology, Tianjin University, Tianjin 300350, China.

3 Department of Physics, Tianjin University, Tianjin 300350, China.

* zsun@dgquanwei.com, yhan@dgquanwei.com, dongbing.chem@nankai.edu.cn, gaohongying@dgquanwei.com

Abstract

Desilylative coupling involving C–Si bond cleavage has emerged as one of the most important synthetic strategies for carbon–carbon/heteroatom bond formation in solution chemistry. However, in on-surface chemistry, C–Si bond cleavage remains a synthetic challenge. Here, we report the implementation of C(sp2)–Si bond cleavage and subsequent C–C bond formation on metal surfaces. The combination of scanning tunneling microscopy and density functional theory calculation successfully reveals that the incorporation of the C–Br group on the arylsilanes is critical to the success of this desilylative coupling reaction on metal surfaces. Our study represents a promising approach for the removal of protecting silyl groups in on-surface chemistry.