Department of Chemistry, Graduate School of Science, Tohoku University, Aoba-ku, Sendai, 980-8578, Japan.
J Am Chem Soc. 2009 Dec 2;131(47):17135-44. doi: 10.1021/ja904525a.
The synthesis, X-ray and spectroscopic analysis, and unusual bonding and structure among heavy group-14 element congeners of allene (heavy allenes) [R(2)M=M'=MR(2); M = M' = Si (1a), M = Si, M' = Ge (1b), M = Ge, M' = Si (1c), and M = M' = Ge (1d)] are comparatively discussed. Using DFT calculations and PMO theory, the origin of the bent and fluxional skeleton of the heavy allenes is ascribed to the Jahn-Teller distortion associated with the effective pi-sigma* mixing (pi-sigma* distortion). This type of distortion is suggested to be a key concept for qualitative description of the unusual bonding of unsaturated compounds of heavy main-group elements.
我们对烯丙基（重烯丙基）[R(2)M=M'=MR(2)；M = M' = Si (1a)，M = Si，M' = Ge (1b)，M = Ge，M' = Si (1c)，和 M = M' = Ge (1d)]的重 14 族元素同系物的合成、X 射线和光谱分析，以及不寻常的键合和结构进行了比较讨论。通过 DFT 计算和 PMO 理论，重烯丙基弯曲和易变骨架的起源归因于与有效 pi-sigma混合（pi-sigma畸变）相关的 Jahn-Teller 畸变。这种类型的畸变被认为是定性描述重主族元素不饱和化合物不寻常键合的关键概念。
