Mechanistic studies on Michael type addition by NMR technique and DFT methods: (CO)(5)W=C(OEt)C2Ph 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 | chinese journal of inorganic chemistry
 |
| 出版日期 | 2006-06-01 |
| 卷号 | 22期号:6页码:1043-1048 |
| 关键词 | Fischer carbene complex Michael addition NMR density functional mechanism |
| 英文摘要 | kinetics of michael type addition using alkynyl carbene complex as substituent was studied by h-1 nmr technique. to either substituted pyrazols or tungsten fischer carbene, the reaction is of first order. and when the substituted groups at 3,5-positions become larger, the reaction rates slow down, with the obvious increase in activation enthalpies and entropies. through density functional calculations, the mechanism of michael type addition was investigated with alkynyl carbene complex as the substrate and 3,5-diphenyl-pyrazole (or 3,5-ditertbutyl-pyrazole) as the nucleophile. it was found that the large substituted groups will increase greatly the activation of step 3, making it larger than that of step 1. accordingly, the rate-determining step should be step 3, which is different from the michael reactions with pyrazoles containing smaller substituted groups or without substituted groups. |
| WOS标题词 | science & technology ; physical sciences |
| 类目[WOS] | chemistry, inorganic & nuclear |
| 研究领域[WOS] | chemistry |
| 关键词[WOS] | fischer carbene complexes ; chemical multitalents ; product distribution ; alkynes ; metal |
| 收录类别 | SCI |
| 语种 | 英语 |
| WOS记录号 | WOS:000238380300014 |
| 公开日期 | 2015-11-17 |
| 源URL | [http://159.226.238.44/handle/321008/140253]  |
| 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, Liaoling, Peoples R China |
| 推荐引用方式 GB/T 7714 | Gu, KC,Yang, G,Zhang, WP,et al. Mechanistic studies on Michael type addition by NMR technique and DFT methods: (CO)(5)W=C(OEt)C2Ph as the substrate[J]. chinese journal of inorganic chemistry,2006,22(6):1043-1048. |
| APA | Gu, KC.,Yang, G.,Zhang, WP.,Liu, XM.,Yu, ZK.,...&Bao, XH.(2006).Mechanistic studies on Michael type addition by NMR technique and DFT methods: (CO)(5)W=C(OEt)C2Ph as the substrate.chinese journal of inorganic chemistry,22(6),1043-1048. |
| MLA | Gu, KC,et al."Mechanistic studies on Michael type addition by NMR technique and DFT methods: (CO)(5)W=C(OEt)C2Ph as the substrate".chinese journal of inorganic chemistry 22.6(2006):1043-1048. |
入库方式： OAI收割
来源：大连化学物理研究所
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