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Original Articles

Single Crystal EPR Studies of Radical Pairs in Dibenzoyl Peroxide

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Pages 133-144 | Received 21 Aug 1978, Published online: 12 Oct 2011

References

  • Recipient of a Dox Fellowship.
  • Box , H. C. , Budzinski , E. E. and Freund , H. G. 1970 . J. Am. Chem. Soc. , 92 : 5305
  • Barchuk , V. I. , Dubinsky , A. A. , Grinberg , O. Ya. and Lebedev , S. Ya. 1975 . Chem. Phys. Lett. , 34 : 476
  • Karch , N. J. , Koh , E. T. , Whitsel , B. L. and McBride , J. M. 1975 . J. Am. Chem. Soc. , 97 : 6729
  • Yim , M. B. , Kikuchi , O. and Wood , D. E. 1978 . J. Am. Chem. Soc. , 100 : 1869
  • McBride , J. M. , Vary , M. W. and Whitsel , B. L. 1978 . ACS Syinp. Ser. , 69 : 208 Organic Free Radicals
  • Sax , M. and McMullan , R. K. 1967 . Acta Cryst. , 22 : 281
  • Atomic coordinates, thermal parameters, and structure factor tables are available on request. We collected X-ray data not to check Reference 7, but to test whether a difference synthesis between data collected before and after photolysis would reveal an oriented product molecularly dispersed in the parent lattice. It has not.
  • When the crystal contains n classes of pairs not related by symmetry, there are 12n observations to determine 5n tensor elements and 3 eulerian angles.
  • McBride , J. M. and Gisler , M. R. 1979 . Molec. Cryst. Liq. Cryst. , 52 : 121
  • In BPO7 the C-O-O-C torsional angle is 90.6°; in acetyl benzoyl peroxide,4 86.6°; in p, p'-dichlorodibenzoyl peroxide,12 81°; in di-β-naphthoyl peroxide,13 90.9°. The o.o'-dihalodibenzoyl peroxides have an angle of 112° in an otherwise centric c∼nformation,14 but bis-2,2,2-triphenylpropionyl peroxide15 is fully centric with a torsional angle of 180°.
  • Caticha-Ellis , S. and Abrahams , S. C. 1968 . Acta Cryst. , B24 : 277
  • Vary , M. W. unpublished work in this laboratory.
  • Gougoutas , J. Z. and Clardy , J. C. 1970 . Acta Cryst. , B26 : 1999
  • Walter , D. W. unpublished work in this laboratory.
  • Vaguely analogous carbonylperoxy-aromatic contacts occur in acetyl benzoyl peroxide,4 p, p'-dichlorodibenzoyl peroxide,12 and di-β-naphthoyl peroxide,13 but these may be fortuitous.
  • The formation of PB pairs at 77 K seems to be a one-photon process.
  • Previously, on the basis of experiments with perdeuterated samples which gave broad lines, we suggested that the approximate site symmetry would conceal the difference between classes of PB pairs formed by loss of different CO2 groups.6 This cannot be so for the present spectra of unlabelled BPO.
  • Kasai , P. H. , Hedaya , E. and Whipple , E. B. 1969 . J. Am. Chem. Soc. , 91 : 4364
  • Eigenvalues of D and g for other pairs are presented in Ref. 6.

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