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Mechanistic studies on Michael type addition by NMR technique and DFT methods: (CO)(5)W=C(OEt)C2Ph as the substrate
Gu, KC; Yang, G; Zhang, WP; Liu, XM; Yu, ZK; Han, XW; Bao, XH
KeywordFischer Carbene Complex Michael Addition Nmr Density Functional Mechanism
Source PublicationCHINESE JOURNAL OF INORGANIC CHEMISTRY
2006-06-01
Volume22Issue:6Pages:1043-1048
Indexed BySCI
SubtypeArticle
WOS HeadingsScience & Technology ; Physical Sciences
WOS SubjectChemistry, Inorganic & Nuclear
WOS Research AreaChemistry
WOS KeywordFISCHER CARBENE COMPLEXES ; CHEMICAL MULTITALENTS ; PRODUCT DISTRIBUTION ; ALKYNES ; METAL
AbstractKinetics 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.
Language英语
WOS IDWOS:000238380300014
Citation statistics
Cited Times:1[WOS]   [WOS Record]     [Related Records in WOS]
Document Type期刊论文
Identifierhttp://cas-ir.dicp.ac.cn/handle/321008/140253
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, Liaoling, Peoples R China
Recommended Citation
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.
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