硅炔（RC≡SiR'）和二硅炔（RSi≡SiR'）：为何键数越少能量越高？
Silynes (RC≡SiR') and Disilynes (RSi≡SiR'): Why Are Less Bonds Worth Energetically More?
作者信息
Danovich David, Ogliaro François, Karni Miriam, Apeloig Yitzhak, Cooper David L, Shaik Sason
机构信息
The Department of Organic Chemistry and The Lise Meitner-Minerva Center for Computational Quantum Chemistry The Hebrew University, 91904 Jerusalem (Israel) Fax: (+972) 2-6584680.
Department of Chemistry and The Lise Meitner-Minerva Center for Computational Quantum Chemistry Technion-Israel Institute of Technology, 32000 Haifa (Israel) Fax: (+972) 4-8294601.
出版信息
Angew Chem Int Ed Engl. 2001 Nov 5;40(21):4023-4026. doi: 10.1002/1521-3773(20011105)40:21<4023::AID-ANIE4023>3.0.CO;2-Z.
Bond stabilization through bending! Valence bond analysis shows that the σ frames of 1-3 (1: E = Si, E' = C; 2: E = E' = Si; 3: E = E' = C) are stabilized by trans bending (B), while π bonding is weakened. In acetylene (3) π bonding overrides the σ frame and establishes a linear molecule (3 L). In contrast, the σ frames dominate in silyne (1) and disilyne (2) and lead to trans-bent structures (1 B and 2 B).
通过弯曲实现键的稳定！价键分析表明，1-3（1：E = Si，E' = C；2：E = E' = Si；3：E = E' = C）的σ骨架通过反式弯曲（B）得以稳定，而π键则被削弱。在乙炔（3）中，π键主导σ骨架并形成线性分子（3L）。相反，在硅炔（1）和乙硅炔（2）中，σ骨架占主导地位并导致反式弯曲结构（1B和2B）。
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