| Sumario: | We study the formation of covalent gold-carbon bonds in benzyltrimethylstannane (CHSn) 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.
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