Synthesis and structures of mono- and binuclear silver(I) complexes with triphenylphosphine and the dodecahydro-closo-dodecaborate anion

Silver complexation with the [B12H12]2− anion was studied in the presence of Ph3P, including reactions performed in the presence of L (L = bipy, phen). Salts with the [B12H12]2− anion as counter ion, and mixed-ligand mononuclear and binuclear silver complexes with the [B12H12]2− anion and Ph3P or Ph3P/L were selectively synthesized by varying reaction conditions. [Display omitted] 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 [Ag2(Ph3P)4[μ-B12H12]] and [Ag2(Ph3P)2L2[μ-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 X-ray diffraction. The structures of single crystals of complexes [Ag(Ph3P)4][Ag(Ph3P)2[B12H12]], (Bu3NH)[Ag(Ph3P)2[B12H12]] · 0.5CH3CN, [Ag(Ph3P)4]2[B12H12] · Ph3P, [Ag2(Ph3P)4[μ-B12H12]] ∙ DMF, [Ag2(Ph3P)2(phen)2[μ-B12H12]], and [Ag2(Ph3P)2(bipy)2[μ-B12H12]] ∙ 0.5CH3CN have been determined by X-ray diffraction.