Toluene-Sandwiched Trinuclear Copper(I) and Silver(I) Triazolates and Phosphine Adducts of Dinuclear Copper(I) and Silver(I) Triazolates

CuI and AgI complexes of the fluorinated triazolate ligand [3,5-(C3F7)2Tz]− have been synthesized using the corresponding metal(I) oxides and the triazole. They form π-acid/base adducts with toluene, leading to [Tol][M3][Tol] ([Tol] = toluene; [M3] = {[3,5-(C3F7)2Tz]Cu}3 or {[3,5-(C3F7)2Tz]Ag}3) type structures. Packing diagrams show the presence of extended chains of the type {[Tol][M3][Tol]}∞, but the intertoluene ring distances are too long for significant π-arene/π-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)2Tz]Cu(PPh3)}2 and {[3,5-(C3F7)2Tz]Ag(PPh3)}2. They feature a six-membered Cu(μ-N−N)2Cu or Ag(μ-N−N)2Ag core with a boat conformation.