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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
论文     
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*()
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*()
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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
收稿日期: 2017-08-30 出版日期: 2017-09-22
中图分类号:  O641  
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)
通讯作者: 周盼盼     E-mail: zhoupp@lzu.edu.cn
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闫超咸
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引用本文:

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, 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. Acta Phys. -Chim. Sin., 2018, 34(5): 497-502, 10.3866/PKU.WHXB201709222.

链接本文:

http://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB201709222        http://www.whxb.pku.edu.cn/CN/Y2018/V34/I5/497

Scheme 1  Reactions of mono-ortho-thioquinones and alkenes via either [2+4] or [4+2] cycloaddition.
Fig 1  The optimized geometries for o-thioquinone (R1) and 1, 3-dienes (R2, R2′) with some atoms numbered.
Fig 2  Proposed mechanism of [2+4] cycloaddition of R1 with R2.
Natural bond orbital fnbo+ fnbo- Reactivityb
R1 BD(1)C1―S1 0.00004 -0.00119 nucleophilic
BD(2)C1―S1 -0.96474 0.92991 electrophilic
BD*(1)C1―S1 -0.00058 -0.00208 inactive
BD*(2)C1―S1 -0.12195 0.02222 electrophilic
BD(1)C2―O2 -0.00025 0.00008 electrophilic
BD(2)C2―O2 -0.97636 0.01660 electrophilic
BD*(1)C2―O2 -0.00021 -0.00034 inactive
BD*(2)C2―O2 -0.10270 0.01291 electrophilic
R2 BD(1)C1–C2 -0.00191 -0.00202 inactive
BD(2)C1―C2 -0.96562 0.96019 electrophilic
BD*(1)C1―C2 0.00046 0.00196 amphiphilic
BD*(2)C1―C2 -0.04328 0.03795 electrophilic
BD(1)C3―C4 -0.00141 -0.00348 inactive
BD(2)C3―C4 -0.96961 0.96052 electrophilic
BD*(1)C3–C4 0.00127 0.00198 amphiphilic
BD*(2)C3―C4 -0.04842 0.03799 electrophilic
R2' BD(1)C1―C2 -0.00209 -0.00273 inactive
BD(2)C1―C2 -0.95650 0.95200 electrophilic
BD*(1)C1―C2 0.00052 0.00206 amphiphilic
BD*(2)C1―C2 -0.05322 0.05365 electrophilic
BD(1)C3―C4 -0.00165 -0.00292 inactive
BD(2)C3―C4 -0.95971 0.94557 electrophilic
BD*(1)C3―C4 0.00113 0.00189 amphiphilic
BD*(2)C3―C4 -0.05703 0.04618 electrophilic
Table 1  NOFFs (unit in electrons) of the C1=S1 and C2=O2 double bonds in R1 and of the C1=C2 and C3=C4 double bonds in R2 and R2', and the reactivities of their natural bond orbitals based on the NOFF values a.
Fig 3  Proposed mechanism of [4+2] cycloaddition of R1 with R2'.
Fig 4  Possible bonding mechanisms for [2+4] cycloaddition of R1 with R2.
Fig 5  Possible bonding mechanisms for [4+2] cycloaddition of R1 with R2'.
Molecule Atom (k) fk+ fk-
R1 C1 0.111 0.011
C2 0.065 0.008
C3 0.009 0.028
C4 0.070 0.023
C5 0.030 0.041
C6 -0.018 -0.004
C7 0.060 0.048
C8 0.023 0.020
C9 0.075 0.073
C10 0.017 0.030
S1 0.123 0.066
O2 0.311 0.543
R2 C1 0.216 0.220
C2 0.088 0.112
C3 0.102 0.089
C4 0.338 0.295
C5 -0.012 -0.032
C6 -0.009 -0.022
R2′ C1 0.220 0.254
C2 0.065 0.098
C3 0.106 0.078
C4 0.339 0.305
C5 -0.010 -0.035
C6 -0.008 -0.025
Table 2  Fukui functions for atoms in the molecules R1, R2 and R2'.
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