Novel Copper(I) Clusters with 2‐(Diphenylphosphanyl)anilide Ligands. Synthesis and Crystal Structures of [Cu6X2(NHR)4] (X = Cl,Br, I; R = C6H4‐2‐PPh2)

Treatment of copper(I) halides CuX (X = Cl, Br, I) with lithium 2‐(diphenylphosphanyl)anilide [Li(HL)] in THF led to the formation of hexanuclear copper(I) complexes [Cu₆X₂(HL)₄] [X = Cl ( 1 ), Br ( 2 ), I ( 3 )]. In compounds 1 – 3 , the copper atoms are in a distorted octahedral arrangement and the amide ligands adopt a μ₃‐κP,κ²N bridging mode. Additionally there are two μ₂‐bridging halide ligands. Each of the [Cu₆X₂(HL)₄] clusters comprises two copper atoms, which are surrounded by two amide nitrogen atoms in an almost linear coordination [Cu–N: 186.2(3)–188.0(3) pm] and four copper atoms, which are connected to an amide N atom, a P atom, and a halogen atom in a distorted trigonal planar fashion [Cu–N: 199.6(3)–202.3(3) pm)].