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An experimental-theoretical approach to the kinetics and mechanism of Michael type addition: alpha,beta-Unsaturated tungsten Fischer carbene complex as the substrate
Gu, KC; Yang, G; Zhang, WP; Liu, XM; Yu, ZK; Han, XW; Bao, XH
KeywordMichael Type Addition Alpha Nmr Beta-unsaturated Fischer Carbene Complexes Density Functional Calculations Activation Barrier
Source PublicationJOURNAL OF ORGANOMETALLIC CHEMISTRY
2006-04-15
DOI10.1016/j.jorganchem.2005.12.063
Volume691Issue:9Pages:1984-1992
Indexed BySCI
SubtypeArticle
WOS HeadingsScience & Technology ; Physical Sciences
WOS SubjectChemistry, Inorganic & Nuclear ; Chemistry, Organic
WOS Research AreaChemistry
WOS KeywordTRANSITION-METAL COMPLEXES ; PHYSICAL ORGANIC-CHEMISTRY ; HYDROTHERMAL STABILITY ; CHEMICAL MULTITALENTS ; PRODUCT DISTRIBUTION ; CHROMIUM ; ALKYNES ; CYCLOPENTADIENES ; INFORMATION ; TEMPERATURE
AbstractThrough 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.
Language英语
WOS IDWOS:000236929300023
Citation statistics
Cited Times:8[WOS]   [WOS Record]     [Related Records in WOS]
Document Type期刊论文
Identifierhttp://cas-ir.dicp.ac.cn/handle/321008/140144
Collection中国科学院大连化学物理研究所
AffiliationChinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Catalysis, Dalian 116023, Liaoning, Peoples R China
Recommended Citation
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.
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