Polymerization of silanes through dehydrogenative Si–Si bond formation on metal surfaces

Element–element double bonds of group 14 elements can be formed in solution, but generally only by applying harsh reductive conditions using sterically highly shielded tetryl halides as precursors. The two-dimensional confinement in surface-assisted polymerization represents a valuable alternative to access such reactive compounds, as it allows shielding of the labile entities without requiring bulky residues and catalytic activation of the reactive groups. Here, we demonstrate Si–Si bond formation in on-surface chemistry. Polymerization upon multiple Si–H bond dissociation and subsequent Si–Si bond formation was achieved on Au(111) and Cu(111) surfaces by using two different monomers, each containing two silicon functional groups (CH3SiH2 or SiH3) attached to an aromatic backbone, leading to polymeric disilenes that interact with the surface. A combination of experimental and theoretical studies corroborates the formation of covalent Si–Si bonds between the long, highly ordered polymer chains with high diastereoselectivity. The reactive Si=Si bonds formally generated via double dehydrogenative coupling are stabilized via covalent Si–surface interaction. On-surface dehydrogenative bond formation between sp3-hybridized carbon atoms usually requires high temperatures. Now, it has been shown that the higher homologue, silicon, can undergo dehydrogenative polymerization at room temperature on metal surfaces. This process creates well-ordered structures on Au(111) and Cu(111), with different stereoselectivity depending on the metal.