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Volumn 75, Issue 17, 2010, Pages 5976-5983

MeLi + LiCl in THF: One Heterodimer and no tetramers

Author keywords

[No Author keywords available]

Indexed keywords

DFT COMPUTATIONS; HETERODIMERS; LITHIUM CHLORIDE; METHYLLITHIUM; MULTINUCLEAR MAGNETIC RESONANCE; NMR DIFFUSION; TETRAMERS;

EID: 77956156445     PISSN: 00223263     EISSN: 15206904     Source Type: Journal    
DOI: 10.1021/jo101282m     Document Type: Article
Times cited : (42)

References (91)
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    • See for instance: Huisgen, R.; Mack, W. Chem. Ber. 1960, 93, 332-340
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    • See for instance in enantioselective protonation
    • See for instance in enantioselective protonation: Yasukata, T.; Koga, K. Tetrahedron: Asymmetry 1993, 4, 35-38
    • (1993) Tetrahedron: Asymmetry , vol.4 , pp. 35-38
    • Yasukata, T.1    Koga, K.2
  • 39
    • 0002174608 scopus 로고
    • For lithium halide salt effects on the reactivity of organometallics, see
    • For lithium halide salt effects on the reactivity of organometallics, see: Chastrette, M.; Amouroux, R. Bull. Soc. Chim. Fr. 1970, 4348-4353
    • (1970) Bull. Soc. Chim. Fr. , pp. 4348-4353
    • Chastrette, M.1    Amouroux, R.2
  • 59
    • 77956143000 scopus 로고    scopus 로고
    • A total amount of 5-10 mol % chloride was measured by potentiometry after hydrolysis of a sample
    • A total amount of 5-10 mol % chloride was measured by potentiometry after hydrolysis of a sample.
  • 60
    • 77956153066 scopus 로고    scopus 로고
    • 6Li signals collapse in a broad signal centered at 0.4 ppm (see Figure 1S of the Supporting Information)
    • 6Li signals collapse in a broad signal centered at 0.4 ppm (see Figure 1S of the Supporting Information).
  • 61
    • 77956165202 scopus 로고    scopus 로고
    • 6Li chemical shifts are given with respect to an external 0.3 M LiCl solution in THF
    • 6Li chemical shifts are given with respect to an external 0.3 M LiCl solution in THF.
  • 64
    • 77956134042 scopus 로고    scopus 로고
    • This rule applies not only to homogeneous hydrocarbons lithium aggregates but also to various mixed lithium aggregates (see ref 4)
    • This rule applies not only to homogeneous hydrocarbons lithium aggregates but also to various mixed lithium aggregates (see ref 4).
  • 66
    • 77956161114 scopus 로고    scopus 로고
    • 6Li dimension. This extra correlation is due to the strong exchange that takes place between LiCl and the new complex, even at 170 K (see the EXSY spectrum, Figure 3S of the Supporting Information). We warmly thank Prof. David Collum (Cornell University) for pointing out the risk of misinterpreting these results leading to erroneous conclusions
    • 6Li dimension. This extra correlation is due to the strong exchange that takes place between LiCl and the new complex, even at 170 K (see the EXSY spectrum, Figure 3S of the Supporting Information). We warmly thank Prof. David Collum (Cornell University) for pointing out the risk of misinterpreting these results leading to erroneous conclusions.
  • 68
    • 0000663851 scopus 로고
    • For leading references on the fluxionality of organolithium derivatives, see
    • For leading references on the fluxionality of organolithium derivatives, see: Fraenkel, G.; Fraenkel, A. M.; Geckle, M. J.; Schloss, F. J. Am. Chem. Soc. 1979, 101, 4745-4747
    • (1979) J. Am. Chem. Soc. , vol.101 , pp. 4745-4747
    • Fraenkel, G.1    Fraenkel, A.M.2    Geckle, M.J.3    Schloss, F.4
  • 70
    • 77956138718 scopus 로고    scopus 로고
    • Spectra simulations were performed with the Daisy Bruker software. See the Supporting Information
    • Spectra simulations were performed with the Daisy Bruker software. See the Supporting Information.
  • 71
    • 77956155109 scopus 로고    scopus 로고
    • 2 J coupling is very small, as confirmed computationally (0.07 Hz)
    • 2 J coupling is very small, as confirmed computationally (0.07 Hz)
  • 72
    • 38549147909 scopus 로고    scopus 로고
    • For a recent review about the determination of molecular size in solution by DOSY experiments, see:;;;, For applications to organolithium derivatives, see:;;; Acc. Chem. Res. 2009, 42, 270-280
    • For a recent review about the determination of molecular size in solution by DOSY experiments, see: Macchioni, A.; Ciancaleoni, G.; Zuccaccia, C.; Zuccaccia, D. Chem. Soc. Rev. 2008, 37, 479-489 For applications to organolithium derivatives, see: Li, D.; Keresztes, I.; Hobson, R.; Williard, P. G. Acc. Chem. Res. 2009, 42, 270-280
    • (2008) Chem. Soc. Rev. , vol.37 , pp. 479-489
    • MacChioni, A.1    Ciancaleoni, G.2    Zuccaccia, C.3    Zuccaccia, D.4    Li, D.5    Keresztes, I.6    Hobson, R.7    Williard, P.G.8
  • 75
    • 77956163677 scopus 로고    scopus 로고
    • The large tailing on the DOSY signals presented cannot be suppressed at the low temperature of these experiments. However, this phenomenon has no effect on the accuracy of the diffusion coefficients since the figures are generated by using curve fitting of signal attenuation data values and are not taken directly from the spectra (see the Supporting Information)
    • The large tailing on the DOSY signals presented cannot be suppressed at the low temperature of these experiments. However, this phenomenon has no effect on the accuracy of the diffusion coefficients since the figures are generated by using curve fitting of signal attenuation data values and are not taken directly from the spectra (see the Supporting Information).
  • 83
    • 0001277236 scopus 로고    scopus 로고
    • We also carried out an analysis in terms of distorsions as described by Fressigné et al. (;;) but did not find any difference between bromide and chloride
    • We also carried out an analysis in terms of distorsions as described by Fressigné et al. (Fressigné, C.; Maddaluno, J.; Giessner-Prettre, C. J. Chem. Soc., Perkin Trans. 2 1999, 2197-2201) but did not find any difference between bromide and chloride.
    • (1999) J. Chem. Soc., Perkin Trans. 2 , pp. 2197-2201
    • Fressigné, C.1    Maddaluno, J.2    Giessner-Prettre, C.3


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.