Reactivity of Indoles through the Eyes of a Charge-Transfer Partitioning Analysis

Citation: OROZCO-VALENCIA Ulises, GÁZQUEZ José L., VELA Alberto. Reactivity of Indoles through the Eyes of a Charge-Transfer Partitioning Analysis[J]. Acta Physico-Chimica Sinica, 2018, 34(6): 692-698. doi: 10.3866/PKU.WHXB201801121 shu

Reactivity of Indoles through the Eyes of a Charge-Transfer Partitioning Analysis

1.
Departamento de Química, Centro de Investigación y de Estudios Avanzados, Av. Instituto Politécnico Nacional 2508, Colonia San Pedro Zacatenco, Ciudad de México, 07360, México
2.
Departamento de Química, Universidad Autónoma Metropolitana-Iztapalapa, Av. San Rafael Atlixco 186, Ciudad de México, 09340, México

通讯作者: VELAAlberto, avela@cinvestav.mx

基金项目:
UOV was supported in part by Conacyt through a doctoral fellowship. JLG thanks Conacyt for grant 237045, and AV thanks Conacyt for grant Fronteras 867

摘要: A global and local charge transfer partitioning model, based on the cornerstone theory developed by Robert G. Parr and Robert G. Pearson, which introduces two charge transfer channels (one for accepting electrons (electrophilic) and another for donating (nucleophilic)), is applied to the reaction of a set of indoles with 4, 6-dinitrobenzofuroxan. The global analysis indicates that the prevalent electron transfer mechanism in the reaction is a nucleophilic one on the indoles, i.e., the indoles under consideration transfer electrons to 4, 6-dinitrobenzofuroxan. Evaluating the reactivity descriptors with exchange-correlation functionals including exact exchange (global hybrids) yields slightly better correlations than those obtained with generalized gradient-approximated functionals; however, the trends are preserved. Comparing the trend obtained with the number of electrons donated by the indoles, and predicted by the partitioning model, with that observed experimentally based on the measured rate constants, we propose that the number of electrons transferred through this channel can be used as a nucleophilicity scale to order the reactivity of indoles towards 4, 6-dinitrobenzofuroxan. This approach to obtain reactivity scales has the advantage of depending on the intrinsic properties of the two reacting species; therefore, it opens the possibility that the same group of molecules may show different reactivity trends depending on the species with which they are reacting. The local model allows systematic incorporation of the reactive atoms based on the their decreasing condensed Fukui functions, and the correlations obtained by increasing the number of reactive atoms participating in the local analysis of the transferred nucleophilic charge improve, reaching an optimal correlation, which in the present case indicates keeping three atoms from the indoles and two from 4, 6-dinitrobenzofuroxan. The atoms selected by this procedure provide valuable information about the local reactivity of the indoles. We further show that this information about the most reactive atoms on each reactant, combined with the spatial distribution of the nucleophilic and electrophilic Fukui functions of both reactants, allows one to propose non-trivial candidates of starting geometries for the search of the transition state structures present in these reactions.

关键词:

English

Reactivity of Indoles through the Eyes of a Charge-Transfer Partitioning Analysis

1.
Departamento de Química, Centro de Investigación y de Estudios Avanzados, Av. Instituto Politécnico Nacional 2508, Colonia San Pedro Zacatenco, Ciudad de México, 07360, México
2.
Departamento de Química, Universidad Autónoma Metropolitana-Iztapalapa, Av. San Rafael Atlixco 186, Ciudad de México, 09340, México

Corresponding author: VELA Alberto, avela@cinvestav.mx

Received Date: 24 November 2017
Accepted Date: 05 January 2018
Revised Date: 29 December 2017
Available Online: 15 June 2018
Fund Project:
UOV was supported in part by Conacyt through a doctoral fellowship. JLG thanks Conacyt for grant 237045, and AV thanks Conacyt for grant Fronteras 867

Abstract: A global and local charge transfer partitioning model, based on the cornerstone theory developed by Robert G. Parr and Robert G. Pearson, which introduces two charge transfer channels (one for accepting electrons (electrophilic) and another for donating (nucleophilic)), is applied to the reaction of a set of indoles with 4, 6-dinitrobenzofuroxan. The global analysis indicates that the prevalent electron transfer mechanism in the reaction is a nucleophilic one on the indoles, i.e., the indoles under consideration transfer electrons to 4, 6-dinitrobenzofuroxan. Evaluating the reactivity descriptors with exchange-correlation functionals including exact exchange (global hybrids) yields slightly better correlations than those obtained with generalized gradient-approximated functionals; however, the trends are preserved. Comparing the trend obtained with the number of electrons donated by the indoles, and predicted by the partitioning model, with that observed experimentally based on the measured rate constants, we propose that the number of electrons transferred through this channel can be used as a nucleophilicity scale to order the reactivity of indoles towards 4, 6-dinitrobenzofuroxan. This approach to obtain reactivity scales has the advantage of depending on the intrinsic properties of the two reacting species; therefore, it opens the possibility that the same group of molecules may show different reactivity trends depending on the species with which they are reacting. The local model allows systematic incorporation of the reactive atoms based on the their decreasing condensed Fukui functions, and the correlations obtained by increasing the number of reactive atoms participating in the local analysis of the transferred nucleophilic charge improve, reaching an optimal correlation, which in the present case indicates keeping three atoms from the indoles and two from 4, 6-dinitrobenzofuroxan. The atoms selected by this procedure provide valuable information about the local reactivity of the indoles. We further show that this information about the most reactive atoms on each reactant, combined with the spatial distribution of the nucleophilic and electrophilic Fukui functions of both reactants, allows one to propose non-trivial candidates of starting geometries for the search of the transition state structures present in these reactions.

Key words:

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沈阳化工大学材料科学与工程学院沈阳 110142

Reactivity of Indoles through the Eyes of a Charge-Transfer Partitioning Analysis

通讯作者: VELAAlberto, avela@cinvestav.mx

English

Reactivity of Indoles through the Eyes of a Charge-Transfer Partitioning Analysis

Corresponding author: VELA Alberto, avela@cinvestav.mx

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

Reactivity of Indoles through the Eyes of a Charge-Transfer Partitioning Analysis

通讯作者: VELAAlberto, avela@cinvestav.mx

English

Reactivity of Indoles through the Eyes of a Charge-Transfer Partitioning Analysis

Corresponding author: VELA Alberto, avela@cinvestav.mx

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

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