Computational Investigation of the Role Played by Rhodium(V) in the Rhodium(III)-Catalyzed ortho-Bromination of Arenes | |
Department | 苏州研究院 |
Zhang, Tao1; Qi, Xiaotian1; Liu, Song1; Bai, Ruopeng1; Liu C(刘超)2; Lan, Yu1; Liu C(刘超) | |
2017 | |
Source Publication | Chemistry - A European Journal |
ISSN | 0947-6539 |
Volume | 23Issue:11Pages:2690-2699 |
Abstract | In this study, M11-L was used to evaluate the feasibility of the formation of rhodium(V) species using the rhodium(III)-catalyzed ortho-bromination of arenes as a model reaction. In most cases for these types of reactions, DFT calculations reveal that the bromination step involves a Br transfer from N-bromosuccinimide to the reacting arylrhodium to form a bromonium intermediate, followed by a Br shift to generate a new C−Br bond, which is more favorable than the previously proposed RhIII/RhV catalytic cycle. The rhodium catalyst remains in its +3 oxidation state throughout. The substituent effects of the reacting arene were studied, and computational results showed that the introduction of electron-donating groups on the reacting arene was favorable for this pathway. In contrast, the inclusion of a strong electron-withdrawing group on the aromatic ring would hinder the formation of a bromonium intermediate. Therefore, the RhIII/RhV catalytic cycle is favorable in cases that involve a RhV intermediate, which is generated by oxidative addition with NBS. In this pathway, the C−Br bond is formed by reductive elimination from the RhV intermediate. Additionally, a distortion–interaction analysis model along the reaction pathway was used to explain the directing-group effects. The results showed that the interaction energy controlled the reactivity because of the difference in electronic nature of various directing groups. |
Keyword | Arenes Bromine Density Functional Calculations Rhodium Reaction Mechanisms |
Subject Area | 物理化学与绿色催化 |
DOI | 10.1002/chem.201605188 |
Funding Organization | the National Natural Science Foundation of China (grant 21372266) |
Indexed By | SCI |
If | 5.317 |
Language | 英语 |
compositor | 第二作者单位 |
Citation statistics | |
Document Type | 期刊论文 |
Identifier | http://ir.licp.cn/handle/362003/21611 |
Collection | 苏州研究院 |
Corresponding Author | Bai, Ruopeng; Lan, Yu; Liu C(刘超) |
Affiliation | 1.Chongqing Univ, Sch Chem & Chem Engn, Chongqing 400030, Peoples R China 2.Chinese Acad Sci, State Key Lab Oxo Synth & Select Oxidat, Suzhou Res Inst, LICP, Lanzhou, Peoples R China |
Recommended Citation GB/T 7714 | Zhang, Tao,Qi, Xiaotian,Liu, Song,et al. Computational Investigation of the Role Played by Rhodium(V) in the Rhodium(III)-Catalyzed ortho-Bromination of Arenes[J]. Chemistry - A European Journal,2017,23(11):2690-2699. |
APA | Zhang, Tao.,Qi, Xiaotian.,Liu, Song.,Bai, Ruopeng.,Liu C.,...&刘超.(2017).Computational Investigation of the Role Played by Rhodium(V) in the Rhodium(III)-Catalyzed ortho-Bromination of Arenes.Chemistry - A European Journal,23(11),2690-2699. |
MLA | Zhang, Tao,et al."Computational Investigation of the Role Played by Rhodium(V) in the Rhodium(III)-Catalyzed ortho-Bromination of Arenes".Chemistry - A European Journal 23.11(2017):2690-2699. |
Files in This Item: | ||||||
File Name/Size | DocType | Version | Access | License | ||
Zhang_et_al-2017-Che(3424KB) | 期刊论文 | 作者接受稿 | 开放获取 | CC BY-NC-SA | View Application Full Text |
Items in the repository are protected by copyright, with all rights reserved, unless otherwise indicated.
Edit Comment