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Ion Pairing in Benzene Anion Solutions. Temperature Dependence of the Linewidth and the Proton Coupling Constant
1.M. G. Townsend and S. I. Weissman, J. Chem. Phys. 32, 309 (1960);
1.J. H. Freed, J. Chem. Phys. 43, 1427 (1965)., J. Chem. Phys.
2.J. H. Freed and R. G. Kooser, J. Chem. Phys. 49, 4715 (1968).
3.J. R. Bolton (private communication).
4.E. de Boer and C. MacLean, J. Chem. Phys. 44, 1334 (1965).
5.K. W. Boddeker, G. Lang, and U. Schindewolf, Angew. Chem. 80 (1968);
5.K. W. Boddeker, G. Lang, and U. Schindewolf, Angew. Chem. Intern. Ed. Engl. 7 (1968).
6.George L. Malinoski and W. H. Bruning, J. Am. Chem. Soc. 89, 5063 (1967). An extensive report on refined rate measurements on benzene, as well as toluene and p‐xylene, is in preparation.
7.G. L. Malinoski, Jr. and W. H. Bruning, Angew. Chem. 80 (1968);
7.G. L. Malinoski, Jr. and W. H. Bruning, Angew. Chem., Intern. Ed. Engl. 7 (1968). In this paper it was assumed that However, much smaller metal coupling constants, plus a temperature‐independent natural linewidth contribution of 0.3 G, will yield good agreement between computer‐simulated and experimental spectra.
8.N. Hirota, J. Phys. Chem. 71, 127 (1967);
8.N. Hirota, J. Am. Chem. Soc. 90, 3611 (1968).
9.R. G. Kooser, thesis, Cornell University, Ithaca, N.Y., 1968.
10.R. G. Lawler (private communication).
11.M. T. Jones, J. Am. Chem. Soc. 88, 174 (1966);
11.R. W. Fessenden and S. Ogawa, J. Am. Chem. Soc. 86, 3591 (1966)., J. Am. Chem. Soc.
12.F. J. Smentowski and G. R. Stevenson, J. Am. Chem. Soc. 89, 5120 (1967).
13.J. R. Bolton has added both RbCl and CsCl to benzenide solutions and has observed line broadening.
14.During initial reduction of by K or Na/K alloy, some visible decomposition of the organic phase occurs. F. S. Dainton et al. (Ref. 16) have shown that DME solutions of K decompose to form alkali‐metal alkoxide salts.
15.The nontemperature‐dependent portion of the benzenide ion linewidth is about 0.3 G. Four Lorenztian lines, of equal intensity, with this linewidth and small would be badly overlapped and result in a nearly unresolvable multiplet exhibiting a strongly non‐Lorenztian line shape. A rapid chemical exchange process, perturbing the spin states in a random fashion, would cause the over‐all shape of the unresolved multiplet to tend toward Lorentzian shape. Indeed, Kooser (Ref. 8) found benzenide hyperfine lines do deviate from Lorenztian shape by small but significant amounts. Observation of metal splittings under such conditions would be exceedingly difficult.
16.A referee has pointed out that the effect might be caused, in part, by decreasing solubility of K or Na metal as temperature increases. F. S. Dainton et al. (J. Chem. Soc. 1960, 4283) have found at in pure DME. However, neither K nor Na show any detectable solubility in THF. In 2:1 THF/DME solutions, we believe over the temperature range of these experiments. Thus, we conclude the effect of dissolved metal on the concentration of in solution, to be small.
17.P. W. Atkins and D. Kivelson, J. Chem. Phys. 44, 169 (1966).
18.A. H. Reddoch, J. Chem. Phys. 41, 444 (1964);
18.A. H. Reddoch, 43, 3411 (1965)., J. Chem. Phys.
19.M. C. R. Symons, J. Phys. Chem. 71, 172 (1967).
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