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.

Azo bond formation on metal surfaces.

The formation of azo compounds via redox cross-coupling of nitroarenes and arylamines, challenging in solution phase chemistry, is achieved by on-surface chemistry. Reaction products are analyzed with a cryogenic scanning tunneling microscope (STM) and X-ray photoelectron spectroscopy (XPS). By using well-designed precursors containing both an amino and a nitro functionality, azo polymers are prepared on surface via highly efficient nitro-amino cross-coupling. Experiments conducted on other substrates and surface orientations reveal that the metal surface has a significant effect on the reaction efficiency. The reaction was further found to proceed from partially oxidized/reduced precursors in dimerization reactions, shedding light on the mechanism that was studied by DFT calculations.

Aryl Triflates in On-Surface Chemistry.

The reactivity of aryl triflates in on-surface C-C coupling is reported. It is shown that the triflate group in aryl triflates enables regioselective homo coupling with preceding or concomitant hydrodetriflation on Cu(111). Three different symmetrical π-systems with two and three triflate functionalities were used as monomers leading to oligomeric conjugated π-systems. The cascade, comprising different intermediates at different reaction temperatures as observed for one of the molecules, proceeds via initial removal of the trifluoromethyl sulfonyl group to give an aryloxy radical which in turn is deoxygenated to the corresponding aryl radical. Thermodynamically driven regioselective 1,2-hydrogen atom transfer leads to a translocated aryl radical which in turn undergoes coupling. For a sterically more hindered bistriflate, where one ortho position was blocked, dehydrogenative coupling occurred at remote position with good regioselectivity. Starting materials, intermediates as well as products were analyzed by scanning tunneling microscopy. Structures and suggested mechanism were further supported by DFT calculations.