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ELECTRON SPIN RESONANCE STUDY OF PHOSPHORANYL RADICALS. PART II.

INTRAMOLECULAR ELECTRON TRANSFER IN PHOSPHORANYL RADICALS. AN E.S.R. STUDY ON THE STEREOISOMERIZATION OF PHENYLPHOSPHORANYL RADICALS IN SOLUTION

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Pages 201-210 | Received 28 Jun 1988, Accepted 18 Aug 1988, Published online: 23 Oct 2006

References

  • Giles , J. R. M. and Roberts , B. P. 1981 . J. Chem. Soc., Perkin Trans. II , : 1211 See e.g
  • de Keijzer , A. E. H. and Buck , H. M. 1987 . Phosphorus and Sulfur , 31 : 203
  • Davies , A. G. , Parrott , M. J. and Roberts , B. P. 1976 . J. Chem. Soc., Perkin Trans. II , : 1066 and references cited therein
  • Bentrude , W. G. 1982 . Acc. Chem. Res. , 15 : 117 E.g. vinyl- and imino(trialkoxy)phosphoranyl radicals, see, and references cited therein
  • Bentrude , W. G. , Moriyama , M. , Mueller , H.-D. and Sopchik , A. E. 1983 . J. Am. Chem. Soc. , 105 : 6051
  • Boekestein , G. , Jansen , E. H. J. M. and Buck , H. M. 1974 . J. Chem. Soc., Chem. Commun. , : 118
  • Mishra , S. P. and Symons , M. C. R. 1974 . J. Chem. Soc., Chem. Commun. , : 606
  • Davies , A. G. , Parrott , M. J. and Roberts , B. P. 1974 . J. Chem. Soc., Chem. Commun. , : 973
  • Symons , M. C. R. 1975 . Mol. Phys. , 30 : 1921
  • Roberts , B. P. and Scaiano , J. C. 1981 . J. Chem. Soc., Perkin Trans. II , 905
  • Hamerlinck , J. H. H. , Schipper , P. and Buck , H. M. 1980 . J. Chem. Soc., Chem. Commun. , : 975
  • Attempts to synthesize additional model compounds in which the remaining oxygen atom in the benzoxa-moiety was replaced by a less electro-negative—N(R) group were not successful. The starting P(III) compound could be detected, but it was too unstable to allow a proper purification. Further experiments regarding the synthesis of compounds in which the five-membered ring in the benzoxaphosphole moiety was expanded to a six membered ring even failed to produce the precursor P(III) compounds
  • Attempts to find evidence of additional free radicals, especially those involving TBP radicals, by investigating a large magnetic field range and using higher microwave power, were not successful
  • Rothuis , R. , Luderer , T. K. J. and Buck , H. M. 1972 . Recl. Trav. Chim. Pays-Bas , 91 : 836
  • Rothuis , R. , Font , J. H. M. , Freide , J. and Buck , H. M. 1973 . Recl. Trav. Chim. Pays-Bas , 92 : 1308
  • Experiments performed with the corresponding phosphate compounds indeed showed that this type of radical is not produced by direct reaction of the peroxide radical with the benzoxa-moiety of the molecule. It is therefore justifiable to conclude that the second radical species is a secondary product resulting from the isomerization of the primary TBP-e radicals
  • Cooper , J. W. , Parrot , M. J. and Roberts , B. P. 1977 . J. Chem. Soc., Perkin Trans. II , 731
  • Denis , R. W. and Roberts , B. P. 1975 . J. Chem. Soc., Perkin Trans. II , 140
  • This is confirmed by a study by Dahl et al.,14 in which the pseudorotation barrier of compound 6 has been determined to amount to 70.3 kJ. mol−1. The magnitude of this barrier does not allow pseudorotation at the temperatures used in this study
  • Dahl , B. M. , Dahl , O. and Trippett , S. 1981 . J. Chem. Soc., Perkin Trans. I , 2239
  • Unfortunately, it was not possible to confirm the assignment of the hyperfine splittings. An ENDOR study of the radical derived from compound 7 would probably give the necessary information for a more definite assignment. The match between the experimental and reconstructed spectrum, however, is so close that despite this minor uncertainty it may be concluded that the reconstructed and experimental spectra are essentially the same
  • GS program, copyright Bruker Spectrospin AG, Switzerland
  • Gilman , H. and Gay , B. J. 1957 . J. Org. Chem. , 22 : 447
  • Hellwinkel , D. 1969 . Chem. Ber. , 102 : 528
  • Hellwinkel , D. 1965 . Chem. Ber. , 98 : 576
  • Allen , D. W. and Millar , I. T. 1969 . J. Chem. Soc. (C) , : 252

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