Conclusions
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1.
A mass spectrometric study has been carried out of the thermal dissociation at high vacuum of organosilicon peroxides, and it has been found that bis(trimethylsilyl) peroxide under these conditions isomerizes to the disiloxane Me2(MeO)SiOSiMe3 (by concerted bond rearrangement), while silyl tert-butyl peroxides undergo free-radical dissociation with further breakdown of the radicals Me3CO, Me3SiO, and Me2ClSiO to Me and Me2C=O (or the corresponding intermediate with the Si=O bond).
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2.
The dimethylsiloxyl radical Me2HSiO, formed in the thermal dissociation of Me2HSi OOCMe3, does not decompose up to 500–600‡C, probably as a result of its isomerization to the dimethyl(hydroxy)silyl radical. The ionization potential of this species (C2H7SiO) has been measured.
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Literature cited
S. Saebo, L. Radom, and H. F. Schaefer, J. Chem. Phys.,78, 845 (1983).
A. H. Zimmermann, R. L. Jackson, B. K. Janousek, and J. I. Brauman, J. Am. Chem. Soc.,100, 4674 (1978); G. B. Ellison, P. C. Engelking, and W. C. Lineberger, J. Phys. Chem.,86, 4873 (1982).
L. V. Luk'yanenko, V. V. Petrenko, A. A. Turovskii, and N. A. Turovskii, Zh. Org. Khim.,18, 705 (1982).
B. W. Gara and B. P. Roberts, J. Chem. Soc., Perkin Trans.,2, 1708 (1977).
V. A. Yablokov, Usp. Khim.,49, 1711 (1980).
V. A. Yablokov, A. V. Ganyushkin, and N. V. Yablokova, Zh. Obshch. Khim.,47, 2553 (1977).
N. D. Kagramanov, A. K. Mal'tsev, M. Yu. Dubinskii, and O. M. Nefedov, Izv. Akad. Nauk SSSR, Ser. Khim., 536 (1983).
L. Batt and M. T. H. Liu, The Chemistry of Peroxides, S. Patai, ed., Wiley, Chichester (1983), pp. 685–710; Y. Ogata, K. Tomizava, and K. Furuka, ibid., pp. 711–775.
V. A. Yablokov, A. N. Sunin, N. B. Yablokova, and A. V. Ganyushkin, Zh. Obshch. Khim.,44, 2446 (1974); E. Bunsel and A. G. Davies, J. Chem. Soc., 1550 (1958); A. V. Tomadze, N. V. Yablokova, V. A. Yablokov, and G. A. Razuvaev, J. Organomet. Chem.,212, 43 (1981); T. G. Barton, S. K. Hoekman, and S. A. Burns, Organometallics,1, 721 (1982).
N. D. Kagramanov, I. O. Bragilevskii, V. A. Yablokov, et al., Izv. Akad, Nauk SSSR, Ser. Khim., 1510 (1986).
K. Újszászy, J. Tamas, N. D. Kagramanov, et al., J. Anal. Appl. Pyrolysis,2, 231 (1980).
J. Tamas and K. Újszászy, Magy. Kern. Fol.,81, 139 (1975).
V. Yu. Orlov, Zh. Obshch. Khim.,37, 2300 (1967).
A. C. Baldwin and D. M. Golden, Chem. Phys. Lett.,60, 108 (1978); A. C. Baldwin, Oxygen and Oxy-radicals in Chemistry and Biology, M. A. J. Rogers and E. L. Powers, eds., Academic Press, New York (1981), p. 551.
P. G. Cookson, A. G. Davies, N. A. Fazal, and B. P. Roberts. J. Am. Chem. Soc.,98, 616 (1976).
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Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1109–1114, May, 1987.
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Kagramanov, N.D., Bragilevskii, I.O., Yablokov, V.A. et al. Formation and reactions of siloxyl free radicals in the vacuum pyrolysis of organosilicon peroxides. Russ Chem Bull 36, 1024–1029 (1987). https://doi.org/10.1007/BF00956360
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DOI: https://doi.org/10.1007/BF00956360