Closely related yet different: a borylene and its dimer are non-interconvertible but connected through reactivity

摘要

The self-stabilizing, tetrameric cyanoborylene [(cAAC)B(CN)]4 (>I, cAAC = 1-(2,6-diisopropylphenyl)-3,3,5,5-tetramethylpyrrolidin-2-ylidene) and its diborene relative, [(cAAC)(CN)BB(CN)(cAAC)] (>II), both react with disulfides and diselenides to yield the corresponding cAAC-supported cyanoboron bis(chalcogenides). Furthermore, reactions of >I or >II with elemental sulfur and selenium in various stoichiometries provided access to a variety of cAAC-stabilized cyanoboron–chalcogen heterocycles, including a unique dithiaborirane, a diboraselenirane, 1,3-dichalcogena-2,4-diboretanes, 1,3,4-trichalcogena-2,5-diborolanes and a rare six-membered 1,2,4,5-tetrathia-3,6-diborinane. Stepwise addition reactions and solution stability studies provided insights into the mechanism of these reactions and the subtle differences in reactivity observed between >I and >II.