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

doi:10.3866/PKU.WHXB201709222

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专刊

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*()

兰州大学化学化工学院，甘肃省有色金属化学与资源利用重点实验室，功能有机分子化学国家重点实验室，兰州730000

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*()

Key Laboratory of Nonferrous Metal Chemistry and Resources Utilization of Gansu Province, State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000, P. R. China

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/Abstract

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f_k1⁺值的k1原子与另一个分子中具有较大f_k2^-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 f_k1⁺ value and atom k2 of another molecule with a large f_k2^- 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

闫超咸,杨帆,吴睿智,周大刚,杨兴,周盼盼. 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[J]. 物理化学学报, 2018, 34(5), 497-502. doi: 10.3866/PKU.WHXB201709222

Chaoxian YAN,Fan YANG,Ruizhi WU,Dagang ZHOU,Xing YANG,Panpan ZHOU. 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[J]. Acta Phys. -Chim. Sin. 2018, 34(5), 497-502. doi: 10.3866/PKU.WHXB201709222

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB201709222

https://www.whxb.pku.edu.cn/CN/Y2018/V34/I5/497

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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

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

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