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.

四种类型的通过1,3-丁二烯基和/或1,3,5,7-辛四烯基片段连接的烯基有机铜(I)聚集体得以在良好的分离收率下选择性合成。这些有机铜(I)聚集体均通过单晶X射线结构分析进行了结构表征。这些前所未有的聚集体，得益于多重Cu-Cu相互作用以及共轭的1,3-丁二烯基或1,3,5,7-辛四烯基桥的稳定作用，能够经历受控的结构转变。1,4-双铜1,3-丁二烯基聚集体3能够有效地转变为聚集体2，而LiI能够将1,3-丁二烯基-1,3,5,7-辛四烯基聚集体4分解为1,3,5,7-辛四烯基聚集体5和1,3-丁二烯基聚集体2。对这些烯基有机铜(I)聚集体的初步反应化学和合成应用也进行了研究。