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The Sigma-Aldrich catalogue of commercially available Grignard reagents includes more than 150 different compounds: ChemFiles, 2007, 7, No 4, 3. In addition, the recent development of methodologies that allows the preparation of highly functionalised Grignard reagents has propelled their application in synthesis, for key references see
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1H NMR analyses of the remaining filtrate showed that its formation was almost quantitative.
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See Supporting Information for full experimental details and copies of NMR spectra
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See Supporting Information for full experimental details and copies of NMR spectra.
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1H NMR spectrum is probably due to removal of some of the magnesium-bound THF molecules when crystals of 1 are dried under vacuum.
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55
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57
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Equilibria of this type have been previously studied in the context of homoleptic alkyl alkali-metal zincates, see
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Equilibria of this type have been previously studied in the context of homoleptic alkyl alkali-metal zincates, see
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We chose 1,2,3,4-tetraphenylnaphthalene (TPhN), 1-phenylnaphthalene (PhN) and tetramethylsilane (TMS) as internal standards for this study
-
We chose 1,2,3,4-tetraphenylnaphthalene (TPhN), 1-phenylnaphthalene (PhN) and tetramethylsilane (TMS) as internal standards for this study.
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77
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2(TMEDA)] using the same internal standards as for 1. Thus, whereas a good fit is observed between its estimated V using DOSY NMR with its calculated V (error -9%), a much greater degree of inaccuracy is obtained between its estimated FW and its actual FW value (error -22%).
-
-
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78
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79953675842
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note
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8]THF were obtained from their optimised geometries. DFT calculations were used to obtain the optimised geometries of the molecules and ions using the Gaussian G03 computational package. The B3LYP density functionals and the 6-311G* basis set were employed in this exercise. For each optimised species a frequency analysis was performed and no imaginary frequencies were obtained.
-
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79
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- cannot be ruled out in the solution constitution of 1 at room temperature (see Supporting Information).
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80
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For an unusual example of a 1,6-addition of a sodium-zincate to benzophenone see
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For an unusual example of a 1,6-addition of a sodium-zincate to benzophenone see:, E. Hevia, G. W. Honeyman, A. R. Kennedy, R. E. Mulvey, J. Am. Chem. Soc. 2005, 127, 13106.
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-] fails to react with benzophenone; however, we believe in this case this lack of reactivity is due to the steric bulk of the tert-butyl groups rather than the tris(alkyl)zinc constitution of the anion in the mixed-metal species.
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For an excellent theoretical study on addition reactions of tris(alkyl)lithium zincates to aldehydes see
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For an excellent theoretical study on addition reactions of tris(alkyl)lithium zincates to aldehydes see:, M. Uchiyama, S. Nakamura, T. Ohwada, M. Nakamura, E. Nakamura, J. Am. Chem. Soc. 2004, 126, 10897.
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2 solution.
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89
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For recent reviews in acid-base catalysis see
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For recent reviews in acid-base catalysis see
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93
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2C(Et)OH resulting from the alkylation reaction (25%), see reference [8].
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