The reactions of electron-rich organosilicon compounds 1,4-bis(trimethylsilyl)-1,4-diaza-2,5-cyclohexadiene (1), 2,3,5,6-tetramethyl-1,4-bis(trimethylsilyl)-1,4-diaza-2,5-cyclohexadiene (2), and 1,1'-bis(trimethylsilyl)-1,1'-dihydro-4,4'-bipyridine (12) with B-amino and B-aryl dihaloboranes afforded a series of novel B=N-bond-containing compounds 3-11 and 13. The B=N rotational barriers of 7 (>71.56 kJ/mol), 10 (58.79 kJ/mol), and 13 (58.65 kJ/mol) were determined by variable-temperature 1H-NMR spectroscopy, thus reflecting different degrees of B=N double bond character in the corresponding compounds. In addition, ring external olefin isomers 11 were obtained by a reaction between 2 and DurBBr2. All obtained B=N-containing products were characterized by multinuclear NMR spectroscopy. Compounds 5, 9, 10a, 11, and 13a were also characterized by single-crystal X-ray diffraction analysis.
Keywords: 1,4-bis(trimethylsilyl)-1,4-diaza-2,5-cyclohexadienes; B=N bond; rotational barrier; salt-free reduction.