1977
DOI: 10.1021/j100519a016
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An electron spin resonance study of the benzene anion radical. A model of its ion pair with alkali metal ions

Abstract: A detailed study of the ESR of potassium, rubidium, and cesium benzenide solutions is described. The g values, metal hyperfine splitting (hfs), and line widths have been measured as a function of solvent, temperature, and metal ion. The g values have been found to depend upon the alkali metal, the temperature, and the solvent. In the case of potassium benzenide, the metal hfs depends upon the temperature and may to a very small extent depend upon the solvent. Estimates of the rubidium and cesium metal hfs are … Show more

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Cited by 22 publications
(10 citation statements)
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“…That this reactivity is not a viable reaction route with toluene is consistent with benzene being easier to reduce than toluene, or viewed from the opposite perspective toluene is more easily oxidised than benzene 40 . The finding that 2K , 2Rb , and 2Cs disproportionate to isolable 4K , 4Rb , and 4Cs , but 2Li and 2Na do not seem to produce 4Li or 4Na , is consistent with previous EPR spectroscopic observations that potassium, rubidium, and caesium reduce benzene, but lithium and sodium seemingly do not 39 , since the formation of the resulting lithium or sodium benzene radical anion complexes would not be favourable.
Fig.
…”
Section: Resultssupporting
confidence: 89%
See 1 more Smart Citation
“…That this reactivity is not a viable reaction route with toluene is consistent with benzene being easier to reduce than toluene, or viewed from the opposite perspective toluene is more easily oxidised than benzene 40 . The finding that 2K , 2Rb , and 2Cs disproportionate to isolable 4K , 4Rb , and 4Cs , but 2Li and 2Na do not seem to produce 4Li or 4Na , is consistent with previous EPR spectroscopic observations that potassium, rubidium, and caesium reduce benzene, but lithium and sodium seemingly do not 39 , since the formation of the resulting lithium or sodium benzene radical anion complexes would not be favourable.
Fig.
…”
Section: Resultssupporting
confidence: 89%
“…Although reaction concentrations are inherently low, immediately quenching a reaction mixture that produces 4K and 6K by freezing the benzene solution and recording an X-band (9.44 GHz) EPR spectrum reveals a weak signal at g = 2.0023 (Supplementary Fig. 38), characteristic of the benzene radical anion (linewidth 14 Gauss) 39 . Allowing the reaction to proceed longer then removing the benzene solvent and recording the X-band EPR spectrum on the solid crude product results in a spectrum with the characteristic absorption at g = 3.74 for 4 K and also a stronger signal at g = 2.0023, Fig.…”
Section: Resultsmentioning
confidence: 99%
“…Formation of R 3 GaPh - and R 3 GaH - in reactions with K or Cs but not Li and a report that K and Cs but not Li react with benzene to form a radical anion provide particularly compelling evidence for the radical anion pathway. Li, K, and Cs can produce R 4 Ga - , however, suggesting a different key step in the pathway leading to R 4 Ga -• .…”
Section: Resultsmentioning
confidence: 99%
“…Nevertheless, there are several observations relative to sample preparation that should be kept in mind when considering the discussion in this section: (1) No reaction of sodium with benzene was evident, with or without laser excitation, in either the infrared or Raman spectra. (2) The organic-rich light-green samples showed product (anion) bands in the infrared and UV-visible spectra but yielded only the neutral benzene Raman spectrum. (3) In the more metal-rich samples, a dominant resonant Raman spectrum emerged slowly, apparently through laser photoionization, with a steady growth of the resonant product bands relative to the neutral benzene bands over periods ranging from a few minutes to 1 h. (4) The infrared and UV-visible spectra reflect a metal-benzene reaction product formed as the sample films were deposited and not the product formed by laser photoexcitation.…”
Section: Resultsmentioning
confidence: 99%