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Volumn 130, Issue 43, 2008, Pages 14179-14188

Microsolvation and 13C-Li NMR coupling

Author keywords

[No Author keywords available]

Indexed keywords

AGGLOMERATION; AGGREGATES; INFORMATION DISSEMINATION; LIGANDS; LITHIUM COMPOUNDS; NUCLEAR MAGNETIC RESONANCE; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; OLIGOMERS; TOLUENE;

EID: 54849442471     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja8026828     Document Type: Article
Times cited : (34)

References (72)
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    • Remenar, J. F.; Collum, D. B. J. Am. Chem. Soc. 1997, 119, 5573-5582 (specifically p 5581).
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    • and Table 2 therein
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    • It should be noted that the lines drawn between Li and R in Chart 1 symbolize connectivities rather than the usual two-electron bonds
    • It should be noted that the lines drawn between Li and R in Chart 1 symbolize connectivities rather than the usual two-electron bonds.
  • 7
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    • Bauer, W.; Feigel, M.; Müller, G.; Schleyer, P. von R. J. Am. Chem. Soc. 1988, 110, 6033-6046 (specifically p 6036).
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    • Details are reported in the Supporting Information
    • Details are reported in the Supporting Information.
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    • For similar identifications of trimers, see the following: a
    • For similar identifications of trimers, see the following: (a) Bauer, W. J. Am. Chem. Soc. 1996, 118, 5450-5455.
    • (1996) J. Am. Chem. Soc , vol.118 , pp. 5450-5455
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    • a = 40.9: Streitwieser, A.; Ciula, J. C.; Krom, J. A.; Thiele, G. J. Org. Chem. 1991, 56, 1074-1076.
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    • a = 40.7: Ahlbrecht, H.; Schneider, G. Tetrahedron 1986, 42, 4729-4741.
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    • This contrasts with the interaction of toluene with monomeric LiN(SiMe3)2 as reported by: Lucht, B. L, Collum, D. J. Am. Chem. Soc. 1996, 118, 2217-2225 (specifically p 2224) and references therein
    • 2 as reported by: Lucht, B. L.; Collum, D. J. Am. Chem. Soc. 1996, 118, 2217-2225 (specifically p 2224) and references therein.
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    • 8]toluene.
    • 8]toluene.
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    • CLi for a trisolvated (a + d = 4) monomer (n = 1); L = 68 Hz would be consistent with the 17/n relation.
    • CLi for a trisolvated (a + d = 4) monomer (n = 1); L = 68 Hz would be consistent with the 17/n relation.
  • 38
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    • Reported coupling constants 1J(13C, 7Li) were converted to 1J(13C, 6Li) values by multiplication with the quotient of the gyromagnetic ratios, γ(6Li)/γ7Li, 1/2.641. Because of the small nuclear quadrupole moment of 6Li, this isotope provides much better conditions than the isotope 7Li for observing the 1JCLi splitting of the 13C α resonance, as demonstrated by: Fraenkel, G, Fraenkel, A. M, Geckle, M. J, Schloss, F. J. Am. Chem. Soc. 1979, 101, 4745-4747
    • α resonance, as demonstrated by: Fraenkel, G.; Fraenkel, A. M.; Geckle, M. J.; Schloss, F. J. Am. Chem. Soc. 1979, 101, 4745-4747.
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    • 40 with multiplet splittings of 4.9 Hz would need an unreasonably high d value of ∼3.6 for L ≈ 55 Hz and hence possibly require another assignment.
    • 40 with multiplet splittings of 4.9 Hz would need an unreasonably high d value of ∼3.6 for L ≈ 55 Hz and hence possibly require another assignment.
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    • Only ∼3 equiv of t-BuOMe in toluene suffices to deaggregate 8 or 12 almost completely, in contrast, two α-aryl- substituted enolates remained purely tetrameric in the poorly coordinating solvent t-BuOMe, according to: Streitwieser, A.; Juaristi, E.; Kim, Y.-J.; Pugh, J. K. Org. Lett. 2000, 2, 3739-3741.
    • Only ∼3 equiv of t-BuOMe in toluene suffices to deaggregate 8 or 12 almost completely, in contrast, two α-aryl- substituted enolates remained purely tetrameric in the "poorly coordinating" solvent t-BuOMe, according to: Streitwieser, A.; Juaristi, E.; Kim, Y.-J.; Pugh, J. K. Org. Lett. 2000, 2, 3739-3741.
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    • CLi values are much more sensitive to the degree of aggregation and number of solvent molecules in the first solvation shell than to thermal motions, according to computational results reported by: de la Lande, A.; Fressigné, C.; Gérard, H.; Maddaluno, J.; Parisel, O. Chem. - Eur. J. 2007, 13, 3459-3469.
    • CLi values are "much more sensitive to the degree of aggregation and number of solvent molecules in the first solvation shell than to thermal motions", according to computational results reported by: de la Lande, A.; Fressigné, C.; Gérard, H.; Maddaluno, J.; Parisel, O. Chem. - Eur. J. 2007, 13, 3459-3469.
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  • 63
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    • We cannot explain the physical basis of eq 1 at this time. For some reflections upon the 17/n relationship, see ref 53 and references therein
    • We cannot explain the physical basis of eq 1 at this time. For some reflections upon the 17/n relationship, see ref 53 and references therein.
  • 64
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    • 2 (a + d = 3) reported on p 5353 in: Jackman, L. M.; Scarmoutzos, L. M. J. Am. Chem. Soc. 1987, 109, 5348-5355. In the spirit of eq 1, however, a tetrasolvated dimer (a + d = 4) would agree with a 7.5/n relation.
    • 2 (a + d = 3) reported on p 5353 in: Jackman, L. M.; Scarmoutzos, L. M. J. Am. Chem. Soc. 1987, 109, 5348-5355. In the spirit of eq 1, however, a tetrasolvated dimer (a + d = 4) would agree with a 7.5/n relation.
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