The ESR spectra of the radical cations of nitrosobenzene, 2,4,6,d‐3‐nitrosobenzene, and 2,4,6,‐tri‐t‐butyl‐nitrosobenzene have been observed by means of continuous electrolysis in organic media. Strong couplings with nitrogen (aN=37.0 Oe) and one meta proton (aH=3.8 Oe) are observed, leading us to propose that they are σ‐radicals; by contrast, the radical—anion of nitrosobenzene is a π radical. The difference is explained on the basis of the electronic structure of the neutral parent compound.
REFERENCES
1.
See, for instance,
A.
Carrington
, Quart. Rev. (London)
17
, 67
(1963
).2.
For a difinition of σ and π radicals, see: M. C. R. Symons, J. Chem. Soc. 1965, 2276;
G.
Berthier
, H.
Lemaire
, A.
Rassat
, and A.
Veillard
, Theoret. Chim. Acta
3
, 213
(1965
).3.
4.
(b) E. J. Geels, R. Konaka, and G. A. Russell, Chem. Commun. 1965, 13. We are indebted to the referee for bringing this paper to our attention.
5.
For the preparation of these new nitroso compounds: G. Cauquis, G. Fauvelot, and J. Rigaudy, unpublished work, 1966.
6.
G. Cauquis and D. Serve, Bull. Soc. Chim. France 1966, 302.
7.
We used a Varian V‐4502‐15 spectrometer. We thank Dr. Servoz‐Gavin for the use of this instrument. For the electrolytic cell, see C. Barry, G. Cauquis, and M. Maurey, Bull. Soc. Chim. France 1966, 2510.
8.
9.
10.
I. R. King and G. W. Kirby, J. Chem. Soc. 1966, 34.
11.
A. P. Best and C. L. Wilson, J. Chem. Soc. 1946, 239.
12.
A. D. Walsh, J. Chem. Soc. 1953, 2288.
13.
D. A. Ramsay, in Determination of Organic Structures by Physical Methods, F. C. Nachod and W. D. Phillips, Eds. (Academic Press Inc., New York, 1962), Vol. 2, p. 245.
14.
15.
16.
17.
P. W. Atkins, N. Keen, and M. C. R. Symons, J. Chem. Soc. 1962, 2873.
18.
W. M. Fox, and W. A. Waters, J. Chem. Soc. 1965, 4628.
19.
D. E. O’Reilly and J. H. Anderson, in Physics and Chemistry of the Organic Solid State, D. Fox, M. M. Labes, and A. Weissberger, Eds. (Interscience Publishers, Inc., New York, 1965), Vol. 2, p. 323.
20.
E. A. Braude and E. S. Waight, in Progress in Stereochemistry, W. Klyne, Ed. (Butterworths, London, 1954), Vol. 1, p. 144.
21.
M. I. Al‐Joboury and D. W. Turner, J. Chem. Soc. 1964, 4434.
22.
23.
This content is only available via PDF.
© 1968 American Institute of Physics.
1968
American Institute of Physics
You do not currently have access to this content.
