Computational Investigation of the Role Played by Rhodium(V) in the Rhodium(III)-Catalyzed ortho-Bromination of Arenes
文献类型:期刊论文
作者 | Zhang, Tao1; Qi, Xiaotian1; Liu, Song1; Bai, Ruopeng1; Liu C(刘超)2![]() ![]() |
刊名 | Chemistry - A European Journal
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出版日期 | 2017 |
卷号 | 23期号:11页码:2690-2699 |
关键词 | arenes bromine density functional calculations rhodium reaction mechanisms |
ISSN号 | 0947-6539 |
通讯作者 | Bai, Ruopeng ; 刘超 ; Lan, Yu |
英文摘要 | 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. |
学科主题 | 物理化学与绿色催化 |
收录类别 | SCI |
资助信息 | the National Natural Science Foundation of China (grant 21372266) |
语种 | 英语 |
WOS记录号 | WOS:000395773600026 |
源URL | [http://210.77.64.217/handle/362003/21611] ![]() |
专题 | 兰州化学物理研究所_苏州研究院 |
通讯作者 | Liu C(刘超) |
作者单位 | 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 |
推荐引用方式 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. |
入库方式: OAI收割
来源:兰州化学物理研究所
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