A novel stable self-assembled chemisorbed layers, providing protection of metal surface against electrooxidation capable of blocking propylene carbonate (PC) electroreduction and Li electrodeposition, were produced from 3-[tris-(2-methoxyethoxy)silyl]-propanethiol (SIS2) on silver. Reflection-absorption infrared spectroscopy (RAIRS) indicated cleavage of the S-H bond upon adsorption of SISI [3-(trimethoxysilyl)-propanethiole] and SIS2 species with the formation of S-Ag bonds on the metal surface. By cyclic voltammetry it was found that the primary adsorbate formed on a Ag electrode at E-ad (between -0.2 and -1.2 V vs. SCE) under-went reductive desorption at E < -1.3 V vs. SCE. From the charge involved in this process, the saturation surface coverage was estimated as 4.2 10(-10) Mol cm(-2). A compact SIS2 layer after long-time aging (hydrolysis and condensation) was electromactive and thus non-desorbable from the electrode surface during the potential cycling. The structures of SIS2 and its complexes with Li+ cations on the Ag surface were calculated and visualized by the AMld semi-empirical method. (c) 2005 Elsevier B.V. All rights reserved.