Silver complexation in the presence of the [B12H12](2) anion and organic ligands Ph3P, bipy, and phen has been studied in organic solvents. By varying the conditions of complexation reactions, regularities have determined under which it is possible to isolate selectively mononuclear silver complexes Cat[Ag(Ph3P)(2)[B12H12]] (Cat = [Ag(Ph3P)(4)](+), (Bu3NH)(+)), binuclear complexes [Ag-2(Ph3P)(4)[mu-B12H12]] and [Ag-2(Ph3P)(2)L-2[mu-B12H12]] (L = phen, bipy), and salt [Ag(Ph3P)(4)](2)[B12H12] with complex cation [Ag(Ph3P)(4)](+). The obtained compounds have been identified by elemental analysis, IR spectroscopy, and Xray diffraction. The structures of single crystals of complexes [Ag(Ph3P)(4)][Ag(Ph3P)(2)[B12H12]], (Bu3NH) [Ag(Ph3P)(2)[B12H12]] center dot 0.5CH(3)CN, [Ag(Ph3P)(4)](2)[B12H12] center dot Ph3P, [Ag-2(Ph3P)(4)[mu-B12H12]] center dot DMF, [Ag-2(Ph3P)(2)(phen)(2)[mu-B12H12]] , and [Ag-2(Ph3P)(2)(bipy)(2)[mu-B12H12]] center dot 0.5CH(3)CN have been determined by X-ray diffraction. (C) 2020 Elsevier Ltd. All rights reserved.