Mechanistic insight into alcohol oxidation mediated by an efficient green Cu-II-bipy catalyst with and without TEMPO by density functional methods
文献类型：期刊论文
| 作者 | Cheng L ; Wang JP ; Wang MY ; Wu ZJ |
| 刊名 | dalton transactions
 |
| 出版日期 | 2010 |
| 卷号 | 39期号:22页码:5377-5387 |
| 关键词 | SELECTIVE AEROBIC OXIDATION O BOND-CLEAVAGE OXIDASE MODEL COMPLEXES GALACTOSE-OXIDASE ELECTRONIC-STRUCTURE END-ON COPPER(II) COMPLEXES THEORETICAL EVIDENCE 2-STATE REACTIVITY MONONUCLEAR COPPER |
| ISSN号 | 1477-9226 |
| 通讯作者 | wu zj |
| 中文摘要 | density functional theory (dft) calculations have been performed to investigate the alcohol oxidation to acetaldehyde catalyzed by the cu-bipy (bipy = 2,2'-bipyridine) catalyst with and without tempo (tempo stands for 2,2,6,60-tetramethylpiperidinyloxy). in the presence of tempo, two mechanisms are proposed, which are (1) tempo and the alcohol coordinate to the cu center and react in the coordination sphere, and (2) the formation of the nitronium cation. on the basis of our calculations, the nitronium cation mechanism can be ruled out. for the case without tempo, it is found that the change of the cu oxidation states (cu-ii <-> cu-i) plays an important role in assisting the catalytic reaction cycle, while the o-2 molecule assists the formation of the product acetaldehyde. in addition, the overall activation barrier with tempo is preferred over the pathway without tempo by 5.2 kcal mol(-1). this is consistent with the experimental observation that the cu-bipy catalyst in the absence of tempo is less efficient when compared with that in the presence of tempo. the difference in mechanism is discussed tentatively based on the molecular orbitals. |
| 收录类别 | SCI收录期刊论文 |
| 语种 | 英语 |
| WOS记录号 | WOS:000278099800023 |
| 公开日期 | 2012-06-06 |
| 源URL | [http://ir.ciac.jl.cn/handle/322003/43702]  |
| 专题 | 长春应用化学研究所_长春应用化学研究所知识产出_期刊论文 |
| 推荐引用方式 GB/T 7714 | Cheng L,Wang JP,Wang MY,et al. Mechanistic insight into alcohol oxidation mediated by an efficient green Cu-II-bipy catalyst with and without TEMPO by density functional methods[J]. dalton transactions,2010,39(22):5377-5387. |
| APA | Cheng L,Wang JP,Wang MY,&Wu ZJ.(2010).Mechanistic insight into alcohol oxidation mediated by an efficient green Cu-II-bipy catalyst with and without TEMPO by density functional methods.dalton transactions,39(22),5377-5387. |
| MLA | Cheng L,et al."Mechanistic insight into alcohol oxidation mediated by an efficient green Cu-II-bipy catalyst with and without TEMPO by density functional methods".dalton transactions 39.22(2010):5377-5387. |
入库方式： OAI收割
来源：长春应用化学研究所
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。