Mechanistic Insights into Palladium-Catalyzed Silylation of Aryl Iodides with Hydrosilanes through a DFT Study | |
Department | 苏州研究院 |
Xu, Zheng1; Xu, Jin-Zhou1; Zhang, Jin1; Zheng, Zhan-Jiang1; Cao, Jian1; Cui, Yu-Ming1; Xu LW(徐利文)1,2; Xu LW(徐利文) | |
The second department | osso国家重点实验室 |
2017 | |
Source Publication | Chemistry - An Asian Journal |
ISSN | 1861-4728 |
Volume | 12Issue:14Pages:1749-1757 |
Abstract | The catalytic cycles of palladium-catalyzed silylation of aryl iodides, which are initiated by oxidative addition of hydrosilane or aryl iodide through three different mechanisms characterized by intermediates R3Si−PdII−H (Cycle A), Ar−PdII−I (Cycle B), and PdIV (Cycle C), have been explored in detail by hybrid DFT. Calculations suggest that the chemical selectivity and reactivity of the reaction depend on the ligation state of the catalyst and specific reaction conditions, including feeding order of substrates and the presence of base. For less bulky biligated catalyst, Cycle C is energetically favored over Cycle A, through which the silylation process is slightly favored over the reduction process. Interestingly, for bulky monoligated catalyst, Cycle B is energetically more favored over generally accepted Cycle A, in which the silylation channel is slightly disfavored in comparison to that of the reduction channel. Moreover, the inclusion of base in this channel allows the silylated product become dominant. These findings offer a good explanation for the complex experimental observations. Designing a reaction process that allows the oxidative addition of palladium(0) complex to aryl iodide to occur prior to that with hydrosilane is thus suggested to improve the reactivity and chemoselectivity for the silylated product by encouraging the catalytic cycle to proceed through Cycles B (monoligated Pd0 catalyst) or C (biligated Pd0 catalyst), instead of Cycle A. |
Keyword | Density Functional Calculations Homogeneous Catalysis Palladium Reaction Mechanisms Silylation |
Subject Area | 物理化学与绿色催化 |
DOI | 10.1002/asia.201700174 |
Funding Organization | the National Natural Science Founder of China (nos. 51303043; 21472031;21503060);Science and Technology Department of Zhejiang Province (2015C31138);Zhejiang Provincial Natural Science Foundation of China (LY17E030003;LY17B030005);Hangzhou Science and Technology Bureau of China (20170533B08;20160432B08) |
Indexed By | SCI |
If | 4.083 |
Language | 英语 |
compositor | 第二作者单位 |
Citation statistics | |
Document Type | 期刊论文 |
Identifier | http://ir.licp.cn/handle/362003/22202 |
Collection | 苏州研究院 羰基合成与选择氧化国家重点实验室(OSSO) |
Corresponding Author | Xu, Zheng; Xu LW(徐利文) |
Affiliation | 1.Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education Hangzhou Normal University, No 1378, Wenyi West Road Science Park of HZNU, Hangzhou (P.R. China) 2.Suzhou Research Institute and State Key Laboratory for Oxo Synthesis and Selective Oxidation Lanzhou Institute of Chemical Physics Chinese Academy of Sciences, (P.R. China) |
Recommended Citation GB/T 7714 | Xu, Zheng,Xu, Jin-Zhou,Zhang, Jin,et al. Mechanistic Insights into Palladium-Catalyzed Silylation of Aryl Iodides with Hydrosilanes through a DFT Study[J]. Chemistry - An Asian Journal,2017,12(14):1749-1757. |
APA | Xu, Zheng.,Xu, Jin-Zhou.,Zhang, Jin.,Zheng, Zhan-Jiang.,Cao, Jian.,...&徐利文.(2017).Mechanistic Insights into Palladium-Catalyzed Silylation of Aryl Iodides with Hydrosilanes through a DFT Study.Chemistry - An Asian Journal,12(14),1749-1757. |
MLA | Xu, Zheng,et al."Mechanistic Insights into Palladium-Catalyzed Silylation of Aryl Iodides with Hydrosilanes through a DFT Study".Chemistry - An Asian Journal 12.14(2017):1749-1757. |
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