The B(C6 F5 )2 -substituted borole 2⋅SMe2 was obtained from the phenyl bis(trimethylsilylethynyl) borane SMe2 adduct (1⋅SMe2 ) by a synthetic sequence containing a rare 1,1-hydroboration reaction. Subsequent thermolysis at 50 °C converted it to the bicyclic borenium/borate zwitterion 3⋅SMe2 . Photolysis of 3⋅SMe2 gave the diboracyclohexadiene derivative 4⋅SMe2 , which after ligand exchange with N,N-dimesitylimidazolylidene and deprotonation gave the 1-bora-3-boratabenzene anion derivative as its potassium salt 6. Some unique follow-up reactions of the unsaturated diboron containing six-membered heterocycles were investigated.
Keywords: Boraalkene; Boraborataarene Anion; Borataalkene; Boron; Framework Rearrangement.
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