Low-Valent, High-Spin Chromium-Catalyzed Cleavage of Aromatic Carbon Nitrogen Bonds at Room Temperature: A Combined Experimental and Theoretical Study
文献类型：期刊论文
| 作者 | Cong, Xuefeng1; Fan, Fei1; Ma, Pengchen3; Luo, Meiming1; Chen, Hui3; Zeng, Xiaoming1,2,4 |
| 刊名 | JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
 |
| 出版日期 | 2017-10-25 |
| 卷号 | 139期号:42页码:15182-15190 |
| 英文摘要 | The cleavage of aromatic carbon nitrogen bonds catalyzed by transition metals is of high synthetic interest because such bonds are common in organic chemistry. However, few metal catalysts can be used to selectively break Caryl)-N bonds in electronically neutral molecules. We report here the first low-valent, high-spin chromium-catalyzed cleavage of Caryl)-N bonds in electronically neutral aniline derivatives at room temperature. By using simple and inexpensive chromium(II) chloride as precatalyst, accompanied by an imino auxiliary, the selective arylative and alkylative C-C coupling of C(aryl)-N bonds can be achieved. Crossover experiments indicate that a low-valent chromium species, formed in situ by reduction of CrCl2 with Grignard reagent, is responsible for the catalytic cleavage of C(aryl)-N bonds. DFT calculations show that facile insertion of the C(aryl) N bond by chromium(0) can take place in a high-spin quintet (S = 2) ground state, whereas the lower-spin singlet (S = 0) and triplet (S = 1) states are inaccessible in energy. It was found that both donation of the sole paired d electrons in the d(6) shell of high-spin chromium(0) to the antibonding orbital of the C(aryl) N bond and the nitrogen ligating interaction to the metal center with its lone pair play important roles in the cleavage of the C(aryl) N bond by the zerovalent chromium species. |
| 语种 | 英语 |
| 源URL | [http://ir.iccas.ac.cn/handle/121111/39155]  |
| 专题 | 化学研究所_光化学实验室 |
| 作者单位 | 1.Sichuan Univ, Coll Chem, Minist Educ, Key Lab Green Chem & Technol, Chengdu 610064, Sichuan, Peoples R China 2.Xi An Jiao Tong Univ, Frontier Inst Sci & Technol, Xian 710054, Shaanxi, Peoples R China 3.Chinese Acad Sci, Inst Chem, CAS Res Educ Ctr Excellence Mol Sci, Key Lab Photochem,BNLMS, Beijing 100190, Peoples R China 4.Nankai Univ, State Key Lab Elementoorgan Chem, Tianjin 300071, Peoples R China |
| 推荐引用方式 GB/T 7714 | Cong, Xuefeng,Fan, Fei,Ma, Pengchen,et al. Low-Valent, High-Spin Chromium-Catalyzed Cleavage of Aromatic Carbon Nitrogen Bonds at Room Temperature: A Combined Experimental and Theoretical Study[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,2017,139(42):15182-15190. |
| APA | Cong, Xuefeng,Fan, Fei,Ma, Pengchen,Luo, Meiming,Chen, Hui,&Zeng, Xiaoming.(2017).Low-Valent, High-Spin Chromium-Catalyzed Cleavage of Aromatic Carbon Nitrogen Bonds at Room Temperature: A Combined Experimental and Theoretical Study.JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,139(42),15182-15190. |
| MLA | Cong, Xuefeng,et al."Low-Valent, High-Spin Chromium-Catalyzed Cleavage of Aromatic Carbon Nitrogen Bonds at Room Temperature: A Combined Experimental and Theoretical Study".JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 139.42(2017):15182-15190. |
入库方式： OAI收割
来源：化学研究所
浏览0
下载0
收藏0
其他版本
除非特别说明，本系统中所有内容都受版权保护，并保留所有权利。