Synthesis and Structures of Group 11 Metal Triazenide Complexes: Ligand Supported Metallophilic Interactions

A homologous and homoleptic series of stable Group 11 metal triazenide complexes with the general formula [M(L′)]_n (M = Cu or Au, n = 2; M = Ag, n = 3) featuring the bulky triazenide ligand N,N′-bis(2,6-di-isopropylphenyl)triazene, L′H, have been prepared by the reaction of Li[L′] with the metal chlorides, CuCl, AgCl, and [(THT)AuCl], respectively, in a 1:1 stoichiometric ratio. The compounds [Cu₂(L′)₂] and [Au₂(L′)₂] crystallized as dimers with M···M separations of 2.4458(4) Å and 2.6762(4) Å, respectively. In comparison, the reaction of AgCl with Li[L′] results in the formation of the tri-silver complex [Ag₃(L′)₃] with Ag···Ag separations of 3.01184(17) Å, 2.95329(17) Å, and 2.92745(16) Å. Attempts to react the parent triazene system L′H with [Cu(Mes)] resulted in the formation of the novel tri-copper system [Cu₃(L′)₂(Mes)]. In all cases the molecular structures of the resultant complexes have been unambiguously determined by single crystal X-ray diffraction experiments.