物理化学学报 >> 2018, Vol. 34 >> Issue (5): 497-502.doi: 10.3866/PKU.WHXB201709222

所属专题: 密度泛函理论中的化学概念特刊

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自然轨道福井函数和成键活性描述符应用于解释苯硫醌和1, 3-二烯的[2+4]和[4+2]环加成反应中的成键机理

闫超咸,杨帆,吴睿智,周大刚,杨兴,周盼盼*()   

  • 收稿日期:2017-08-30 发布日期:2018-01-24
  • 通讯作者: 周盼盼 E-mail:zhoupp@lzu.edu.cn
  • 基金资助:
    国家自然科学基金(21403097);中央高校基本科研业务费专项资金(lzujbky-2016-45)

Application of Natural Orbital Fukui Functions and Bonding Reactivity Descriptor in Understanding Bond Formation Mechanisms Underlying [2+4] and [4+2] Cycloadditions of o-Thioquinones with 1, 3-Dienes

Chaoxian YAN,Fan YANG,Ruizhi WU,Dagang ZHOU,Xing YANG,Panpan ZHOU*()   

  • Received:2017-08-30 Published:2018-01-24
  • Contact: Panpan ZHOU E-mail:zhoupp@lzu.edu.cn
  • Supported by:
    the National Natural Science Foundation of China(21403097);the Fundamental Research Funds for the Central Universities, China(lzujbky-2016-45)

摘要:

苯硫醌与脂肪族烯烃可以发生[2+4]和[4+2]环加成反应。为了解释这些环加成反应中的成键过程,本文使用了自然轨道福井函数(NOFF)与成键活性描述符。自然轨道福井函数揭示了苯硫醌和脂肪族烯烃的键或轨道的亲电性,表明电子供体的成键轨道和电子受体的反键/成键轨道之间发生了电子转移,然后成环,在这一过程中有两个共价键形成,得到了环状产物。成键活性描述符表明共价键比较容易在一个分子中具有较大fk1+值的k1原子与另一个分子中具有较大fk2-值的k2原子之间形成。自然轨道福井函数与成键活性描述符都可以有效解释苯硫醌与1, 3-二烯之间的[2+4]与[4+2]环加成反应的机理。

关键词: 福井函数, 自然轨道福井函数, 成键活性描述符, 环加成反应, 亲核/亲电进攻

Abstract:

o-Thioquinones can undergo either [2+4] or [4+2] cycloaddition reactions with acyclic dienes. To illustrate the bonding processes in these cycloadditions, the natural orbital Fukui function (NOFF) and bonding reactivity descriptor have been employed. The electrophilicity of a bond or an orbital in the o-thioquinone as well as in the acyclic diene has been found using the NOFF, which suggests that electron transfer takes place from an electron-donating bonding orbital to an electron-accepting antibonding/bonding orbital, leading to the cyclic product via the formation of a circular loop and two covalent bonds. The bonding reactivity descriptor shows that covalent bonds readily form between atom k1 of one molecule with a large fk1+ value and atom k2 of another molecule with a large fk2- value. Both the NOFF and the bonding reactivity descriptor are efficient tools for interpreting the mechanism underlying the [2+4] and [4+2] cycloaddition between o-thioquinones and acyclic dienes.

Key words: Fukui function, Natural orbital Fukui function (NOFF), Bonding reactivity descriptor, Cycloaddition, Nucleophilic/electrophilic attack

MSC2000: 

  • O641