Exploring the Synthesis and Coordination Chemistry of Pentafluorophenylcopper: Organocopper Polyanions and Coordination Networks

[CuC6F5]4 is a thermally stable and soluble compound with suitable reactivity for synthetic applications in organic and inorganic chemistry. Here the synthesis of [CuC6F5]4 is explored in different solvents and followed by in situ 19F NMR spectroscopy. The importance of solvent choice during the synthesis from Grignard reagent C6F5MgBr is highlighted, with a range of magnesium cuprate species identified and isolated when THF is used as solvent (rather than Et2O), including [Cu­(C6F5)2]− and the remarkable organocopper polyanion ([Cu5(C6F5)7]2–)∞. The coordination chemistry of [CuC6F5]4 with 1,4-dioxane is investigated in solution and in the solid state, with an extended coordination network, [CuC6F5]4(dioxane), structurally resolved for the first time. This structure reveals interwoven linear and zig-zag chains featuring dioxane donors unusually coordinating to adjacent Cu sites of some of the [CuC6F5]4 tetramers.