Trimethyltin-Mediated Covalent Gold–Carbon Bond Formation

We study the formation of covalent gold− carbon bonds in benzyltrimethylstannane (C10H16Sn) deposited on Au in ultra-high-vacuum conditions. Through X-ray photoemission spectroscopy and X-ray absorption measurements, we find that the molecule fragments at the Sn−benzyl bond when exposed to Au surfaces at temperatures as low as −110 °C. The resulting benzyl species is stabilized by the presence of Au(111) but only forms covalent Au−C bonds on more reactive Au surfaces like Au(110). We also present spectroscopic proof for the existence of an electronic “gateway” state localized on the Au−C bond that is responsible for its unique electronic properties. Finally, we use DFT-based nudged elastic band calculations to elucidate the crucial role played by the under-coordinated Au surface in the formation of Au−C bonds.