Cu-I and Ag-I complexes of the fluorinated triazolate ligand [3,5-(C3F7)(2)Tz](-) have been synthesized using the corresponding metal(l) oxides and the triazole. They form pi-acid/base adducts with toluene, leading to [Tol][M-3](Tol] ([Tol] = toluene; [M-3] = {[3,5(C3F7)(2)Tz]Cu}(3) or {[3,5-(C3F7)(2)Tz]Ag}(3)) type structures. Packing diagrams show the presence of extended chains of the type {[Tol][M-3][Tol]}(infinity), but the intertoluene ring distances are too long for significant pi-arene/pi-arene contacts. These copper and silver triazolates react with PPh3 (at a 1:1 metal ion/P molar ratio), leading to dinuclear {[3,5-(C3F7)(2)Tz]Cu(PPh3)}(2) and {[3,5-(C3F7)(2)Tz]Ag(PPh3)}(2). They feature a six-membered Cu (mu-N-N)(2)Cu or Ag(mu-N-N)(2)Ag core with a boat conformation.