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题名: An experimental-theoretical approach to the kinetics and mechanism of Michael type addition: alpha,beta-Unsaturated tungsten Fischer carbene complex as the substrate
作者: Gu, KC;  Yang, G;  Zhang, WP;  Liu, XM;  Yu, ZK;  Han, XW;  Bao, XH
关键词: alpha,beta-unsaturated Fischer carbene complexes ;  Michael type addition ;  NMR ;  density functional calculations ;  activation barrier
刊名: JOURNAL OF ORGANOMETALLIC CHEMISTRY
发表日期: 2006-04-15
DOI: 10.1016/j.jorganchem.2005.12.063
卷: 691, 期:9, 页:1984-1992
收录类别: SCI
文章类型: Article
WOS标题词: Science & Technology ;  Physical Sciences
类目[WOS]: Chemistry, Inorganic & Nuclear ;  Chemistry, Organic
研究领域[WOS]: Chemistry
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.
关键词[WOS]: TRANSITION-METAL COMPLEXES ;  PHYSICAL ORGANIC-CHEMISTRY ;  HYDROTHERMAL STABILITY ;  CHEMICAL MULTITALENTS ;  PRODUCT DISTRIBUTION ;  CHROMIUM ;  ALKYNES ;  CYCLOPENTADIENES ;  INFORMATION ;  TEMPERATURE
语种: 英语
WOS记录号: WOS:000236929300023
Citation statistics: 
内容类型: 期刊论文
URI标识: http://cas-ir.dicp.ac.cn/handle/321008/140144
Appears in Collections:中国科学院大连化学物理研究所_期刊论文

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作者单位: 1.Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Catalysis, Dalian 116023, Liaoning, Peoples R China

Recommended Citation:
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.
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