The 鈥淗ockey Sticks鈥?Effect Revisited: The Conformational and Electronic Properties of 3,7-Dithia-1,5-diazabicyclo[3.3.1]nonane from the QTAIM Perspective

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• 作者：I. S. Bushmarinov ; I. V. Fedyanin ; K. A. Lyssenko ; V. L. Lapteva ; S. A. Pisarev ; V. A. Palyulin ; N. S. Zefirov ; M. Yu. Antipin
• 刊名：Journal of Physical Chemistry A
• 出版年：2011
• 出版时间：November 17, 2011
• 年：2011
• 卷：115
• 期：45
• 页码：12738-12745
• 全文大小：958K
• 年卷期：v.115,no.45(November 17, 2011)
• ISSN：1520-5215

文摘

The conformational effects in bicyclo[3.3.1]nonanes, while thoroughly studied, have not yet received the full theoretical explanation. R. F. W. Bader鈥檚 quantum theory of atoms in molecules presents unique opportunities for studying the stereoelectronic interactions (SEI) and weak intramolecular bonding leading to these effects. Here, we report the study of 3,7-dithia-1,5-diazabicyclo[3.3.1]nonane by means of the topological analysis of the calculated (MP2(full)/6-311++G**) and experimental (X-ray derived) charge density to reveal the origins of the so-called 鈥渉ockey sticks鈥?effect observed in similar compounds. A new explanation of the relative stability of bicyclo[3.3.1]nonane conformers based on the analysis of the QTAIM atomic energies is given. The H路路路H and S路路路S interactions in bicyclo[3.3.1]nonane and its dithia derivatives are shown to be significant factors contributing to the differences in the relative stability of the conformers.