One-pot condensation of a bicyclo[1.1.1]pentasilane through elimination of iodotrimethylsilane assisted by a lewis base
Development of efficient bond formation reactions remains important in organic and main-group-element chemistry. Herein, we report the metal-free one-pot condensation reaction of 1-iodo-3-trimethylsilyl-substituted bicyclo[1.1.1]pentasilane (BPS) in the presence of 4-(dimethylamino)pyridine (DMAP) providing oligomers of BPS, persila[n]staffanes (n = 2, 3), which involves the successive Si?Si bond formation reaction accompanied by the concomitant formation of iodotrimethylsilane (TMSI) in the form of a DMAP complex. The computational study suggests that the formation of a pentasila[1.1.1]propellane?DMAP complex resulting from the elimination of TMSI from the BPS is a key intermediate.
Persilastaffanes: Design, synthesis, structure, and conjugation between silicon cages
By stepwise catenation of bicyclo[1.1.1]pentasilane units persila[n]staffanes (n=1, 2, and 3) were synthesized as air-stable colorless crystals. A remarkable red-shift of the UV/Vis absorption bands with increasing number of bicyclo[1.1.1]pentasilane unit