An experimental-theoretical approach to the kinetics and mechanism of Michael type addition: alpha,beta-Unsaturated tungsten Fischer carbene complex as the substrate
文献类型：期刊论文
| 作者 | Gu, KC; Yang, G; Zhang, WP; Liu, XM; Yu, ZK; Han, XW; Bao, XH |
| 刊名 | journal of organometallic chemistry
 |
| 出版日期 | 2006-04-15 |
| 卷号 | 691期号:9页码:1984-1992 |
| 关键词 | alpha Michael type addition NMR density functional calculations activation barrier beta-unsaturated Fischer carbene complexes |
| 英文摘要 | through variable-temperature h-1 and c-13 nmr experiments and density functional calculations, the kinetics and mechanism of michael type addition were investigated using alkynyl carbene a as the substrate. the two conformers of substrate a were distinguished from the h-1 and c-13 nmr spectra, and the calculated results showed that the syn-conformer is more stable than the anti- by 6.5 kj mol(-1) with the activation barrier between these two conformers as 62.5 kj mol(-1). the full reaction mechanism of michael type addition was first presented to us, which differs from the previous solely based on the kinetic studies. it contains three elementary steps (see the scheme): (1) formation of c-8-n-2 bond via transition state ts1. (2) conformation conversion from in-1 to in-2, which is very important but ignored before. (3) intramolecular proton transfer via transition state ts2 forming the product. the first step is rate determining with an activation barrier of 73.0 kj mol(-1), very close to the experimental value of 89.6 kj mol(-1). the product p is dominant over p' in population contrary to the situation of tautomer b' over b, which is caused by larger activation barriers to p' and the less stabilities of structures related to b' from the first transition state to the product. |
| WOS标题词 | science & technology ; physical sciences |
| 类目[WOS] | chemistry, inorganic & nuclear ; chemistry, organic |
| 研究领域[WOS] | chemistry |
| 关键词[WOS] | transition-metal complexes ; physical organic-chemistry ; hydrothermal stability ; chemical multitalents ; product distribution ; chromium ; alkynes ; cyclopentadienes ; information ; temperature |
| 收录类别 | SCI |
| 语种 | 英语 |
| WOS记录号 | WOS:000236929300023 |
| 公开日期 | 2015-11-17 |
| 源URL | [http://159.226.238.44/handle/321008/140144]  |
| 专题 | 大连化学物理研究所_中国科学院大连化学物理研究所 |
| 作者单位 | Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Catalysis, Dalian 116023, Liaoning, Peoples R China |
| 推荐引用方式 GB/T 7714 | Gu, KC,Yang, G,Zhang, WP,et al. An experimental-theoretical approach to the kinetics and mechanism of Michael type addition: alpha,beta-Unsaturated tungsten Fischer carbene complex as the substrate[J]. journal of organometallic chemistry,2006,691(9):1984-1992. |
| APA | Gu, KC.,Yang, G.,Zhang, WP.,Liu, XM.,Yu, ZK.,...&Bao, XH.(2006).An experimental-theoretical approach to the kinetics and mechanism of Michael type addition: alpha,beta-Unsaturated tungsten Fischer carbene complex as the substrate.journal of organometallic chemistry,691(9),1984-1992. |
| MLA | Gu, KC,et al."An experimental-theoretical approach to the kinetics and mechanism of Michael type addition: alpha,beta-Unsaturated tungsten Fischer carbene complex as the substrate".journal of organometallic chemistry 691.9(2006):1984-1992. |
入库方式： OAI收割
来源：大连化学物理研究所
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