Silylation of carbon surfaces through the electrochemical reduction of 2,2′-bipy·R 3 SiCl adducts

Abstract

To cite this version:Mamadou Dieng, Jacques Simonet, Viatcheslav Jouikov. Silylation of carbon surfaces through the electrochemical reduction of 2,2'-bipy×R 3 SiCl adducts. Electrochemistry Communications, Elsevier, 2015, 53, pp.33-36. <10.1016/j.elecom.2015.02.008>. <hal-01132166>A C C E P T E D M A N U S C R I P T ACCEPTED MANUSCRIPT AbstractElectrochemical reduction of complexes of monochlorosilanes with redox-active ligands such as 2,2'-bipy occurs in one-electron fashion at moderately negative potentials, E @ -1 V vs SCE (in CH 3 CN/0.1 M Bu 4 NBF 4 ), leading to silyl radicals. These radicals, trapped with a-phenyl-N-tbutyl-nitrone and characterized as spin-adducts by ESR spectroscopy, add to carbon interfaces (glassy carbon, graphite) providing an efficient method of covalent Si-C silylation of such surfaces. Silylated interfaces were studied by voltammetry, EIS, SEM, EDS, and FTIR spectroscopy.

General Concepts and Recent Advances in the Electrochemical Transformation of Chloro‐ and Hydrosilanes

“… Electrochemical generation of detectable silyl radical anions via bipy coordination and subsequent silylation of unsaturated C=C bonds at the glassy carbon (GC) cathode surface [142] …”

“…Another exciting publication by Jouikov and co‐workers, [142] describes the combination of 2,2’‐bipyridine (bipy) complexation of chlorosilanes with the trapping strategy using reactive C=C double bonds. Bipy as an adduct forms a hexacoordinated state with monochlorosilanes (Scheme 19) and chlorogermanes [143] .…”

“…Electrochemical generation of detectable silyl radical anions via bipy coordination and subsequent silylation of unsaturated C=C bonds at the glassy carbon (GC) cathode surface. [142] Scheme 20. Reductive silylation of dichalcogenides via the generation of strong chalcogenide nucleophiles (X = S, Se): [104] a) silylation via nucleophilic bond formation by chalcogenide anions, b) kinetic investigations showing the favored SiÀ Se bond formation due to higher nucleophilicity.…”