高等学校化学学报 ›› 1998, Vol. 19 ›› Issue (10): 1650.

• 论文 • 上一篇    下一篇

芳氢与配位硫原子之间(sp2C-H…S)的分子内氢键

施继成1, 温庭斌1, 李文洁1, 吴达旭1, 郑瑜1, 刘秋田1, 康北笙2   

  1. 1. 中国科学院福建物质结构研究所结构化学国家重点实验室, 福州, 350002;
    2. 中山大学化学化工学院, 物理化学研究所, 广州, 510275
  • 收稿日期:1997-07-15 出版日期:1998-10-24 发布日期:1998-10-24
  • 通讯作者: 施继成,男,31岁,博士.
  • 作者简介:施继成,男,31岁,博士.
  • 基金资助:

    国家自然科学基金(批准号:29333033)资助课题.

Intramolecular Hydrogen Bond Between Aromatic Hydrogen and Coordinated Sulfur Atom(sp2C-H…S)

SHI Ji-Cheng1, WEN Ting-Bin1, LI Wen-Jie1, WU Da-Xu1, ZHENG Yu1, LIU Qiu-Tian1, Kang Bei-Sheng2   

  1. 1. State Key Laboratory of Structural Chemistry and Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, 350002;
    2. Institute of Physical Chemistry, Zhongshan University, Guang zhou, 510275
  • Received:1997-07-15 Online:1998-10-24 Published:1998-10-24

摘要: 化合物(Et4N)2[Pd2(mp)2(Hmp)2](1)(H2mp=2-巯基苯酚)的1HNMR谱中芳氢H16的峰出现在δ8.79处,与预测值(δ7.1)相差1.7,这是由于H16与配位硫S2原子之间存在弱相互作用,即新型的sρ2C-H…S之间的氢键作用.原子间距离C16…S2(0.361pm)和H16…S2(0.295pm)分别小于相应原子的范德华半径之和(0.370pm和0.305pm),C16-H16…S2角为128.1°,证明了这种新型氢键的存在.此外,在分子振动光谱中观察到这种氢键的作用使得芳氢υC-H出现在低于3000cm-1处.通过与类似物[Pd2(PPh3)2(Hmp)2Cl2](2)的比较,以及1在DMSO溶剂中仍然保持O-H…O和C-H…S这2种氢键的事实,表明C-H…S之间的作用,对1的配体Hmp中的苯环与Pd2S2平面之间的夹角偏离90°可能是有贡献的.

关键词: 分子内C-H&hellip, S氢键, 钯(Ⅱ)配合物, 2-巯基苯酚

Abstract: Weak interaction between the H16 atom of aromatic hydrocarbon and the coordinated S2 atom, a new type of hydrogen bond sp2 C—H…S, has been suggested in explaining the phenomenon of the 1H NMR H16 peak of the compound(Et4N)2 Pd 2(mp)2(Hmp)2 (H2mp=2-mercaptophenol) appearing at δ 8.79 which is 1.7 lower than the expected value δ 7.1. The distances of C16…S2(0.361 pm) and H16…S2(0.295 pm) lowing the sum of the van der Waals radii(0.325 pm) for the corresponding atoms, respectively, demonstrates the existence of the hydrogen bond. In addition, it has been observed that the C Hof aromatic hydrocarbon shifts to 2998 cm-1 resulting from the sp2 C H…Shydrogen interaction. Comparison with the structure of the analogues compound Pd2(PPh3)2(Hmp)2Cl2 and the remaining of the O—H…Oand C—H…Shydrogen bonds even in DMSOsuggest that the torsion angle between the phenyl linking to the bridging sulfur atom and Pd2S2 plane deviated from 90° may be contributed partially from the C H…Shydrogen bonding.

Key words: Intramolecular C—H…S hydrogen bond, Pd(Ⅱ) complex, 2-Mercaptophenol

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