Alkyl chains are covalently attached onto metal surfaces by indirect reduction of the bromoalkyl derivative (RBr). This indirect reaction involves the formation (by spontaneous or electrochemical reduction of the 2,6-dimethylbenzenediazonium salt) of a sterically hindered aryl radical that abstracts a Br atom from RBr but does not react with the surface. This crossover reaction furnishes an alkyl radical that reacts with the surface. Starting from 6-bromohexanoic acid, carboxylic functionalized gold surfaces are prepared. "Layer-by-layer" assemblies are built from these surfaces and present some ionic selectivity.