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Effect of Electronegativity and Magnetic Anisotropy of Substituents on C13 and H1 Chemical Shifts in CH3X and CH3CH2X Compounds
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9.The value of for methane gas, recently measured by M. Lipsicas‐Lipschitz [Ph.D. thesis, University of British Columbia, Vancouver (1960)], is 0.02 sec, and that of ethane gas, 0.2 sec.
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18.Electronegativities used are so‐called “best values” compiled by D. E. Pritchard and H. A. Skinner, Chem. Rev. 55, 745 (1955).
18.They differ little from the original Pauling scale [L. Pauling, Nature of the Chemical Bond (Cornell University Press, Ithaca, New York, 1960)].
19.The electronegativity correlation line in this plot is obviously not as well established as in the corresponding proton plot. Lauterbur6 has previously pointed out a nearly linear correlation of the resonances of tetramethyl compounds with the electronegativity of the central atom. The inclusion of the ion in such a correlation may be questioned. The fact that its resonance falls near the correlation line is surprising in itself. The small positive deviation of the point appears real. If the correlation line were made to pass through the and points, the indicated anisotropy contribution for would then obviously be much too large. The correlation line shown in Fig. 5 gives the best overall consistency with the experimental data, but its approximate nature must be emphasized.
20.The direction and relative magnitudes of the shifts in these compounds parallel the corresponding proton shifts of the hydride molecules, and HF, for which anisotropy contributions have been calculated theoretically. (See reference 17.)
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27.J. R. Cavanaugh and B. P. Dailey, J. Chem. Phys. 34, 1099 (1961). We are greatly indebted to the authors for communicating their results to us prior to publication.
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