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 [Cu-2(L')(2)] and (Au-2(L')(2)] crystallized as dimers with M center dot center dot center dot M separations of 2.4458(4) angstrom and 2.6762(4) angstrom, respectively. In comparison, the reaction of AgCl with Li[L'] results in the formation of the tri-silver complex [Ag-3(L')(3)] with Ag center dot center dot center dot Ag separations of 3.01184(17) angstrom, 2.95329(17) angstrom, and 2.92745(16) angstrom. Attempts to react the parent triazene system L'H with [Cu(Mes)) resulted in the formation of the novel tri-copper system [Cu-3(L')(2)(Mes)]. In all cases the molecular structures of the resultant complexes have been unambiguously determined by single crystal X-ray diffraction experiments.