Nature of "Hydrogen Bond" in the Diborane-Benzene Complex: Covalent, Electrostatic, or Dispersive?

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• 作者：Hongzhi Li ; Donghong Min ; Sheldon G. Shore ; William N. Lipscomb ; Wei Yang
• 刊名：Inorganic Chemistry
• 出版年：2007
• 出版时间：May 14, 2007
• 年：2007
• 卷：46
• 期：10
• 页码：3956 - 3959
• 全文大小：126K
• 年卷期：v.46,no.10(May 14, 2007)
• ISSN：1520-510X

文摘

Motivated by the recent discovery of unusual "hydrogen bonding"-like interaction between a borane system andbenzene molecules in a molecular crystal, we carried out quantum mechanical calculations on a model complex,diborane-benzene cluster. The aim is to understand the nature of this unique interaction, which is expected to playan essential role in this novel class of molecular crystals. As analyzed in the present study, the interaction betweendiborane and benzene is special in the following aspects: (1) this interaction is mostly dispersive; (2) the observedpseudodirectionality with one of the diborane bridge hydrogen directed toward the benzene centroid minimizes thevan der Waals contact; and (3) in the "hydrogen bond" map, this interaction is located in a unique region, whichis presently populated by a few known molecular complexes with very different chemical characteristics. It is anticipatedthat the results from the present analysis will provide meaningful guidance for molecular engineering with diborane-benzene as a building block and for stabilization of this and possible other hydrogen bonds by dispersive contributions.