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(<b>L′</b>)]<sub><i>n</i></sub> (M = Cu or Au, <i>n</i> = 2; M = Ag, <i>n</i> = 3) featuring the bulky triazenide ligand <i>N,N</i>′-bis(2,6-di-isopropylphenyl)triazene, <b>L′</b>H, have been prepared by the reaction of Li[<b>L′</b>] with the metal chlorides, CuCl, AgCl, and [(THT)AuCl], respectively, in a 1:1 stoichiometric ratio. The compounds [Cu<sub>2</sub>(<b>L′</b>)<sub>2</sub>] and [Au<sub>2</sub>(<b>L′</b>)<sub>2</sub>] 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[<b>L′</b>] results in the formation of the tri-silver complex [Ag<sub>3</sub>(<b>L′</b>)<sub>3</sub>] 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 <b>L′</b>H with [Cu(Mes)] resulted in the formation of the novel tri-copper system [Cu<sub>3</sub>(<b>L′</b>)<sub>2</sub>(Mes)]. In all cases the molecular structures of the resultant complexes have been unambiguously determined by single crystal X-ray diffraction experiments.