Cui Chunming, Olmstead Marilyn M, Power Philip P
Department of Chemistry, University of California at Davis, 95616 USA.
J Am Chem Soc. 2004 Apr 28;126(16):5062-3. doi: 10.1021/ja0318481.
The first reactions of the "digermyne" Ar'GeGeAr' (1, Ar' = C6H3-2,6-Dipp2, Dipp = C6H3-2,6-iPr2) with alkynes are reported. 1 reacts with 1 equiv of H5C6CCC6H5 to afford the 1,2-digermacyclobutadiene 2 in high yield, while it reacts with 2 equiv of the less hindered alkyne Me3SiCCH to yield an unexpected bicyclic compound 3. Molecular structures of 2 and 3 were determined by X-ray crystallography. A possible mechanism for the formation of 3 is discussed. The high reactivity of 1, even at room temperature, emphasizes the fundamental differences between the GeGe and CC multiple bonds.
报道了“二锗炔”Ar'GeGeAr'（1，Ar' = C6H3-2,6-Dipp2，Dipp = C6H3-2,6-iPr2）与炔烃的首次反应。1与1当量的H5C6CCC6H5反应，以高产率得到1,2-二锗环丁二烯2，而它与2当量位阻较小的炔烃Me3SiCCH反应，生成一种意想不到的双环化合物3。通过X射线晶体学确定了2和3的分子结构。讨论了形成3的可能机理。1即使在室温下也具有高反应活性，这突出了GeGe和CC多重键之间的根本差异。
