Isolable and Well-Defined Butadienyl Organocopper(I) Aggregates: Facile Synthesis, Structural Characterization, and Reaction Chemistry

Four
types of alkenyl organocopper­(I) aggregates linked by 1,3-butadienyl
and/or 1,3,5,7-octatetraenyl moieties were selectively realized in
good isolated yields. All these organocopper­(I) aggregates were structurally
characterized by single-crystal X-ray structural analysis. These unprecedented
aggregates, stabilized by multiple Cu–Cu interactions and the
conjugated 1,3-butadienyl or 1,3,5,7-octatetraenyl bridges, could
undergo controlled structural transformations. The 1,4-dicopper 1,3-butadienyl
aggregate 3 could be efficiently transformed to aggregate 2, while LiI could disaggregate the 1,3-butadienyl-1,3,5,7-octatetraenyl
aggregate 4 to 1,3,5,7-octatetraenyl aggregate 5 and 1,3-butadienyl aggregate 2. Preliminary
reaction chemistry and synthetic applications of these organocopper­(I)
aggregates were also investigated.