Abstract: | Bidentate boron Lewis acids based on 1,8‐diethynylanthracene were synthesised in two steps by initial stannylation of the terminal alkynes and subsequent tin–boron exchange with different chloroboranes. The reactions were very selective, and the target compounds were obtained in high purity and good to excellent yields. Complexation experiments of 1,8‐bis[(diphenylboranyl)ethynyl]anthracene with nitrogen bases (pyridine, pyrimidine, TMEDA) afforded three stable adducts, which were structurally characterised by X‐ray diffraction. Competition experiments demonstrated the selective exchange of guests, and quantum‐chemical calculations provided information on their energetics. NMR experiments at low temperature gave insight into the dynamic behaviour of the TMEDA adduct. |