Anion radicals of a series of aromatic compounds (C6H5CN, C6H5COOEt, anthracene, 9,10-dimethyl-, 9,10-diphenyl- and 9-phenylanthracene, pyrene and naphthalene) react with trialkyl chlorosilanes (RRRSiCl)-R-1-R-2-Si-3 (R1-3 = Me, Et; R-1,R-2 = Me, R-3 = t-Bu) in multiple ways, following classical bimolecular schemes. The ratio of one-electron transfer (ET) to a two-electron process (S(N)2-like nucleophilic attack of the reduced form of mediator on the chlorosilane, with k(2) congruent to 10(2)-10(8) M-1 s(-1)) is inversely related to the steric availability of Si for nucleophilic displacement reactions. The nucleophilic substitution pathway mainly results in mono- and disilylated aromatic products. Paralleling the electrochemical data with DFT calculations, the role of silicophilic solvent (DMF) in S-N processwas shown to be quite complex because of its involvement into coordination extension at silicon, dynamically modifying energetics of the process along the reaction coordinate. Although 2,2'-bipyridine also forms delocalized persistent anion radicals, they do not induce neither ET nor SN reactions in the same manner as aromatic mediators. Silicophilicity of 2,2'-bipyridine being superior to that of DMF, a R3SiCl center dot bipy complex of hypercoordinated silicon with electroactive ligand was formed instead, whose reduction requires about 1 V less negative potentials than bipyridine itself. (C) 2015 Elsevier Ltd. All rights reserved.