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Volumn 126, Issue 32, 2004, Pages 9993-10002

Mechanism of silver-mediated di-tert-butylsilylene transfer from a silacyclopropane to an alkene

Author keywords

[No Author keywords available]

Indexed keywords

BUTENES; COMPLEXATION; CONCENTRATION (PROCESS); NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; OLEFINS; REACTION KINETICS;

EID: 4043141373     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja0306563     Document Type: Article
Times cited : (70)

References (138)
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    • -1, and ΔS‡ = -15 eu. (c) A Hammett study revealed that cycloaddition was under entropic control and occurred through a concerted, electrophilic attack of di-tert-butylsilylene on the alkene.
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    • For leading references to the coordination of Lewis bases with silylenes, refer to (a) Steele, K. P.; Weber, W. P. J. Am. Chem. Soc. 1980, 102, 6095-6097.
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    • For recent reports of other silver or gold catalyzed reactions, see (a) Longmire, J. M.; Wang, B.; Zhang, X. J. Am. Chem. Soc. 2002, 124, 13400-13401.
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    • For additional metal-catalyzed reactions of silacycles see: (a) Ohshita, J.; Ishikawa, M. J. Organomet. Chem. 1991, 407, 157-165.
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    • For studies detailing the role of the electronic nature of phosphine ligands in metal phosphine complexes, refer to: (a) Rahman, M. M.; Liu, H. Y.; Prock, A.; Giering, W. P. Organometallics 1987, 6, 650-658.
    • (1987) Organometallics , vol.6 , pp. 650-658
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    • note
    • 64 for further details.
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    • note
    • Refer to the experimental and Supporting Information sections for further details.
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    • 4043058163 scopus 로고    scopus 로고
    • note
    • 2OTf to produce product would exhibit a rate law inconsistent with the kinetic data (zero order in styrene concentration would be predicted). For more details and analyses of other less-likely mechanisms refer to the Supporting Information.
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    • 4043060973 scopus 로고    scopus 로고
    • note
    • 1H NMR spectrum of cyclohexene in the presence of silylsilver complex 8 (relative to cyclohexene without silver) did not provide evidence for the coordination of cyclohexene to silver.
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    • note
    • 2(Cl).
  • 111
    • 4043063797 scopus 로고    scopus 로고
    • note
    • 1H} NMR spectrum sharpened, and the area of the doublet at 6.23 ppm was noticeably smaller. Examination of the NMR tube, however, revealed the formation of extensive precipitation. Further analysis at this (or lower) temperatures was hampered by the insolubility of the intermediates.
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    • note
    • 29Si NMR spectrum, the smaller broad singlet at δ 4.52 could either be another product that does not contain silicon or evidence of the formation of an oligomeric silicon phospine compound.
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    • note
    • 2SiOTf IR spectra.
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    • 0000877315 scopus 로고
    • While the isolation of any distinct products was not possible, no spectroscopic evidence for the formation of any Si-H products was observed. For references on various oligomeric silicon products resulting from the decomposition of silylenes refer to: (a) Masamune, S.; Murakami, S.; Tobita, H. Organometallics 1983, 2, 1464-1466.
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    • Stepwise reactions that involve charged intermediates, such as the hydration and bromination of styrene, are typified by large negative p values. For example: hydration p = -4 (by Schubert, W. M.; Lamm, B.; Keefe, J. R. J. Am. Chem. Soc. 1964, 86, 4727-4729) and bromination p = -4.3 (by Dubois, J. E.; Schwarcz, A. Tetrahedron Lett. 1964, 5, 2167-2173).
    • (1964) J. Am. Chem. Soc. , vol.86 , pp. 4727-4729
    • Schubert, W.M.1    Lamm, B.2    Keefe, J.R.3
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    • Stepwise reactions that involve charged intermediates, such as the hydration and bromination of styrene, are typified by large negative p values. For example: hydration p = -4 (by Schubert, W. M.; Lamm, B.; Keefe, J. R. J. Am. Chem. Soc. 1964, 86, 4727-4729) and bromination p = -4.3 (by Dubois, J. E.; Schwarcz, A. Tetrahedron Lett. 1964, 5, 2167-2173).
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    • note
    • The shielding or deshielding of vinylic protons (Δδ ppm) between an alkene and a metal-alkene complex was used to generalize the amount of π electron density present on the alkene moiety.
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    • For the Dewar-Chatt model of metal-olefin bonding, see: (a) Dewar, M. J. S. Bull. Soc. Chim. Fr. 1951, 18, C71-C79.
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    • Electron-rich 2,2′-bipyridine ancillary ligands on copper(I) alkene complexes augmented the electron density present on the bound alkene (relative to free alkene) through increased π back-donation in the copper(I)-ethylene bonding. See: Munakata, M.; Kitagawa, S.; Kosome, S.; Asahara, A. Inorg. Chem. 1986, 25, 2622-2627.
    • (1986) Inorg. Chem. , vol.25 , pp. 2622-2627
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    • note
    • nOTf.
  • 135
    • 4043161546 scopus 로고    scopus 로고
    • note
    • Since a limited temperature range (40 °C) was used to determine the activation parameters, caution should be used in drawing firm conclusions from them.
  • 136
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    • The uncertainties in the activation parameters were calculated from the error propagation formulas derived by Girolami and Binsch. See: (a) Morse, P. M.; Spencer, M. D.; Wilson, S. R.; Girolami, G. S. Organometallics 1994, 13, 1646-1655.
    • (1994) Organometallics , vol.13 , pp. 1646-1655
    • Morse, P.M.1    Spencer, M.D.2    Wilson, S.R.3    Girolami, G.S.4


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.