Bidentate Boron Lewis Acids: Selectivity in Host-Guest Complex Formation

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.