物理化学学报 >> 2015, Vol. 31 >> Issue (2): 227-236.doi: 10.3866/PKU.WHXB201411061

热力学,动力学和结构化学 上一篇    下一篇

双二茂铁基吡咯衍生物电荷交互通道

胡宇强, 竺宁, 韩利民   

  1. 内蒙古工业大学化工学院, 呼和浩特 010051
  • 收稿日期:2014-08-05 修回日期:2014-11-05 发布日期:2015-01-26
  • 通讯作者: 韩利民 E-mail:hanlimin_442@hotmail.com,hanlimin@imut.edu.cn,huyuqiang@imut.edu.cn
  • 基金资助:

    内蒙古自治区自然科学基金(2012ZD01), 内蒙古工业大学自然科学基金(X201207)和内蒙古自治区研究生科研创新基金(B20131012802)资助项目

Channel of Electronic Interactions in Diferrocenyl Pyrrole Derivatives

HU Yu-Qiang, ZHU Ning, HAN Li-Min   

  1. College of Chemical Engineering, Inner Mongolia University of Technology, Hohhot 010051, P. R. China
  • Received:2014-08-05 Revised:2014-11-05 Published:2015-01-26
  • Contact: HAN Li-Min E-mail:hanlimin_442@hotmail.com,hanlimin@imut.edu.cn,huyuqiang@imut.edu.cn
  • Supported by:

    The project was supported by the Natural Science Foundation of Inner Mongolia, China (2012ZD01), Natural Science Foundation of Inner Mongolia University of Technology, China (X201207), and Graduate Student Research Innovation Foundation of Inner Mongolia, China (B20131012802).

摘要:

以二茂铁炔烃为原料通过“一锅法”环加成反应合成了一系列2,5-双二茂铁基-1-苯基-吡咯衍生物, 包括: 2,5-双二茂铁基-1-(3-三氟甲基苯基)-吡咯(1), 2,5-双二茂铁基-1-(4-氟苯基)-吡咯(2), 2,5-双二茂铁基-1-苯基-吡咯(3), 2,5-双二茂铁基-1-(4-乙基苯基)-吡咯(4)和2,5-双二茂铁基-1-(4-乙氧基苯基)-吡咯(5), 使用元素分析, 傅里叶变换红外(FTIR)光谱, 质谱(MS)和核磁共振(NMR)等手段对化合物进行了结构表征. 采用循环伏安法(CV), 密度泛函理论(DFT)模拟计算研究了苯基上取代基对双二茂铁间电荷交互的影响. 研究发现第一氧化电位(Ea1), 峰电位差(ΔE)与取代基的哈米特常数(σ), 吡咯1H NMR的化学位移(δ), 吡咯N原子自然轨道(NBO)电荷之间存在显著线性关联; 同时发现, N原子电荷密度升高, 双二茂铁间电荷交互能力减弱, N原子电荷密度降低, 双二茂铁间电荷交互能力提高. 因此这类双二茂铁基吡咯衍生物中N原子电荷密度对双二茂铁间电荷交互起着关键的影响作用.

关键词: 双二茂铁基, 吡咯衍生物, 电荷交互通道

Abstract:

2,5-Diferrocenyl-1-(3-trifluorom-ethylphenyl)-pyrrole (1), 2,5-diferrocenyl-1-(4-fluorophenyl)-pyrrole (2), 2,5-diferrocenyl-1-phenyl pyrrole (3), 2,5-diferro-cenyl-1-(4-ethylphenyl)-pyrrole (4), and 2,5-diferrocenyl- 1-(4-ethoxyphenyl)-pyrrole (5) were prepared by the one-pot cycloaddition reaction of ferrocenyl alkyne. The 2,5-diferrocenyl-1-phenyl-1-pyrrole derivatives were characterized by elemental analysis, Fourier-transform infrared (FTIR) spectroscopy, mass spectrometry (MS), and nuclear magnetic resonance (NMR) spectroscopy. The influence of substituents at the phenyl moiety on the electronic interaction was studied using cyclic voltammetry (CV) and density functional theory (DFT) calculations. A linear relationship was observed between the first oxidation potential (Ea1), oxidation potential difference (ΔE) with Hammett constant (Hammett σ) of the substituent, pyrrole 1H NMR chemical shift (δ), and pyrrole N natural bond orbital (NBO) charge. A high N charge density weakened the electronic interaction, and vice versa. Electron transfer between the two ferrocenyl units of these diferrocenyl pyrrole derivatives was influenced by the N charge density.

Key words: Diferrocenyl, Pyrrole derivative, Channel of electronic interaction

MSC2000: 

  • O646