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Kinetics and Spectroscopy of Carbenes and Biradicals pp 143–211Cite as

The Chemistry, Kinetics, and Mechanisms of Triplet Carbene Processes in Low-Temperature Glasses and Solids

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Abstract

In the early 1960s, Closs and Hutchison at the University of Chicago(1) and Trozzolo and Wasserman(2) at Bell Laboratories demonstrated the utility of matrix isolation EPR spectroscopy in the study of triplet carbenes. Triplet carbenes are, of course, highly reactive intermediates formed upon photolysis of diazo compounds or diazirines. As such, they cannot be isolated and analyzed by conventional methods as can kinetically stable species. By photochemically preparing a carbene in a rigid matrix at low temperature, one hopes to impart a long lifetime (minutes to hours) to the species of interest, thereby enabling its characterization by EPR spectroscopy. These rigid matrices are easily prepared by simply freezing a solution of, for example, a diazo precursor in a suitable solvent to 77 K.

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References

  1. G. L. Gloss, in: Carbenes (R. A. Moss and J. Jones, Jr., eds.), Vol. 2, Wiley, New York.

    Google Scholar 

  2. A. M. Trozzolo and E. Wasserman, in: Carbenes (R. A. Moss and M. Jones, Jr., eds.), Wiley, New York (1975), p. 185.

    Google Scholar 

  3. C. A. Hutchison, Jr. and B. W. Mangum, J. Chem. Phys. 19, 952 (1958);

    Article  Google Scholar 

  4. A. Carrington and A. D. McLachlin, Introduction to Magnetic Resonance, Harper and Row, New York (1967).

    Google Scholar 

  5. S. I. Weissman, Acc. Chem. Res. 6, 233 (1973).

    Article  CAS  Google Scholar 

  6. S. I. Weissman, J. Chem. Phys. 19, 1189 (1958).

    Article  Google Scholar 

  7. W. J. Baron, M. R. DeCamp, M. E. Hendrick, M. Jones, Jr., R. H. Levin, and M. B. Sohn, Carbenes Vol. 1 Wiley, New York (1973).

    Google Scholar 

  8. W. Kirmse, Carbene Chemistry, Academic Press, New York (1971).

    Google Scholar 

  9. G. M. J. Schmidt, Solid State Photochemistry, Verlag-Chemie, Weinheim, DDR (1976);

    Google Scholar 

  10. J. R. Scheffer, Acc. Chem. Res. 13, 283 (1980).

    Article  CAS  Google Scholar 

  11. D. E. Doetschman and C. A. Hutchison, Jr., J. Chem. Phys. 56, 3964 (1972);

    Article  CAS  Google Scholar 

  12. J. M. McBride, Jr., Acc. Chem. Res. 16, 304 (1983).

    Article  CAS  Google Scholar 

  13. R. A. Moss and U.-H. Dolling, J. Am. Chem. Soc. 93, 954 (1971).

    Article  CAS  Google Scholar 

  14. A. M. Trozzolo, R. W. Murray, and E. Wasserman, J. Am. Chem. Soc. 84, 4991 (1962);

    Article  Google Scholar 

  15. E. Wasserman, A. M. Trozzolo, W. A. Yager, and R. W. Murray, J. Am. Chem. Soc. 40, 2408 (1964);

    CAS  Google Scholar 

  16. L. Barash, E. Wasserman, and W. A. Yager, J. Am. Chem. Soc. 89, 3931 (1967)

    Article  CAS  Google Scholar 

  17. R. E. Moser, J. M. Fritsch, and C. N. Mathews, J. Chem. Soc. Chem. Commun. 1967, 770.

    Google Scholar 

  18. T. A. Baer and C. D. Gutsche, J. Am. Chem. Soc, 93, 5180 (1971).

    Article  CAS  Google Scholar 

  19. R. A. Moss and J. K. Huselton, J. Am. Chem. Soc 100, 1314 (1978).

    Article  CAS  Google Scholar 

  20. R. A. Moss and M. A. Joyce, J. Am. Chem. Soc 100, 4475 (1978).

    Article  CAS  Google Scholar 

  21. R. A. Moss and M. A. Joyce, J. Am. Chem. Soc. 99, 1262 (1977); see correction: J. Am. Chem. Soc. 99, 7399 (1977).

    Article  CAS  Google Scholar 

  22. H. Tomioka, Y. Ozaki, and Y. Izawa, Chem. Lett. 1982, 843.

    Google Scholar 

  23. H. Tomioka, Y. Ozaki, Y. Koyabu, and Y. Izawa, Tetrahedron Lett. 23, 1917 (1982).

    Article  CAS  Google Scholar 

  24. T. G. Savino, K. Kanakarajan, and M. S. Platz, J. Org. Chem. 51, 1305 (1986).

    Article  CAS  Google Scholar 

  25. P. S. Skell and M. S. Cholod, J. Am. Chem. Soc. 91, 713 (1969).

    Google Scholar 

  26. K. N. Houk, N. G. Rondan, and J. Mareda, Tetrahedron 41, 1555 (1985);

    Article  CAS  Google Scholar 

  27. I. R. Gould, N. J. Turro, J. Butcher, Jr., C. Doubleday, Jr., N. P. Hacker, G. F. Lehr, R. A. Moss, D. P. Cox, W. Guo, R. C. Munjal, L. A. Perez, and M. Fedorynski, Tetrahedron 45, 1587 (1985).

    Article  Google Scholar 

  28. F. H. Westheimer, Chem. Rev. 61, 265 (1961).

    Article  CAS  Google Scholar 

  29. H. Tomioka, J. Am. Chem. Soc 101, 256 (1979).

    Article  CAS  Google Scholar 

  30. R. L. Barcus, C. M. Hadel, L. J. Johnston, M. S. Platz, T. G. Savino, and J. C. Scaiano, J. Am. Chem. Soc. 108, 3928 (1986);

    Article  CAS  Google Scholar 

  31. L. M. Hadel, V. M. Maloney, M. S. Platz, W. F. McGimpsey, and J. C. Scaiano, J. Phys. Chem. 90, 2488 (1986);

    Article  CAS  Google Scholar 

  32. D. Griller, L. M. Hadel, A. S. Nazran, M. S. Platz, P. C. Wong, T. G. Savino, and J. C. Scaiano, J. Am. Chem. Soc. 106, 2227 (1984).

    Article  CAS  Google Scholar 

  33. H. Tomioka, M. Itoh, S. Yamakawa, and Y. Izawa, J. Am. Chem. Soc. Perkin Trans.2 1980, 603.

    Article  Google Scholar 

  34. R. S. Hutton and H. D. Roth, J. Am. Chem. Soc. 100, 4324 (1978).

    Article  CAS  Google Scholar 

  35. H. Tomioka, S. Suzuki, and Y. Izawa, Chem. Lett. 1980, 293.

    Google Scholar 

  36. H. D. Roth, Acc Chem. Res. 10, 85 (1977).

    Article  CAS  Google Scholar 

  37. H. Tomioka and Y. Izawa, J. Am. Chem. Soc. 99, 6128 (1977).

    Article  CAS  Google Scholar 

  38. H. Tomioka, T. Miwa, S. Suzuki, and Y. Izawa, Bull. Chem. Soc Jpn. 53, 753 (1980).

    Article  CAS  Google Scholar 

  39. H. Tomioka, S. Suzuki, and Y. Izawa, J. Am. Chem. Soc 104, 3156 (1982).

    Article  CAS  Google Scholar 

  40. S. Oikawa and M. Tsuda, J. Am. Chem. Soc. 107, 1940 (1985).

    Article  CAS  Google Scholar 

  41. L. B. Harding, H. B. Schlegel, R. Krishnan, and J. A. Pople, J. Phys. Chem.. 84, 3394 (1980)

    Article  CAS  Google Scholar 

  42. see also J. Am. Chem. Soc. 105, 6389 (1983).

    Google Scholar 

  43. J. C. Scaiano and L. C. Stewart, J. Am. Chem. Soc. 105, 3609 (1983).

    Article  CAS  Google Scholar 

  44. R. L. Barcus, M. S. Platz, and J. C. Scaiano, J. Phys. Chem. 91, 695 (1987).

    Article  CAS  Google Scholar 

  45. C. P. Baskin, C. F. Bender, C. W. Bauschlicher, Jr., and H. F. Schaefer III, J. Am. Chem. Soc. 96, 2709 (1974).

    Article  CAS  Google Scholar 

  46. C. N. Bauschlicher, Jr. and H. F. Schaefer III, J. Am. Chem. Soc. 98, 3072 (1976).

    Article  CAS  Google Scholar 

  47. H. Tomioka, G. W. Griffin, and K. Nishiyama, J. Am. Chem. Soc 101, 6009 (1979).

    Article  CAS  Google Scholar 

  48. M. S. Platz, V. P. Senthilnathan, B. B. Wright, and C. W. McCurdy, Jr., J. Am. Chem. Soc 104, 6494 (1982).

    Article  CAS  Google Scholar 

  49. B. B. Wright and M. S. Platz, J. Am. Chem. Soc 106, 4175 (1984).

    Article  CAS  Google Scholar 

  50. See C. W. Bauschlicher, Jr. and I. Shavitt, J. Am. Chem. Soc. 100, 739 (1978).

    Article  CAS  Google Scholar 

  51. P. F. Zittel, G. B. Ellison, S. V. O’Neill, E. Herbst, C. W. Lineberger, and W. P. Reinhardt, J. Am. Chem. Soc. 98, 3731 (1976).

    Article  CAS  Google Scholar 

  52. C. A. Hutchison, Jr. and B. E. Kohler, J. Chem. Phys. 51, 3327 (1969).

    Article  CAS  Google Scholar 

  53. E. Levya, R. L. Barcus, and M. S. Platz, J. Am. Chem. Soc. 108, 7786 (1986).

    Article  Google Scholar 

  54. J. Zayas and M. S. Platz, J. Am. Chem. Soc. 107, 7065 (1985).

    Article  CAS  Google Scholar 

  55. J. M. McBride, Jr. and M. J. Tremelling, J. Org. Chem. 37, 1073 (1972).

    Article  Google Scholar 

  56. H. C. Chang, R. Popovitz-Biro, M. Lahav, and L. Leiserowitz, J. Am. Chem. Soc. 104, 614 (1982).

    Article  CAS  Google Scholar 

  57. H. Tomioka, T. Inagaki, and Y. Izawa, J. Chem. Soc. Chem. Commun. 1976, 1023.

    Google Scholar 

  58. H. Tomioka, T. Inagaki, S. Nakamura, and Y. Izawa, J. Chem. Soc., Perkin Trans. 1 1979, 130.

    Article  Google Scholar 

  59. H. Tomioka, H. Okuno, and Y. Izawa, J. Chem. Soc., Perkin Trans.2 1980, 1636.

    Article  Google Scholar 

  60. H. Tomioka, H. Okuno, and Y. Izawa, J. Org. Chem. 45, 5278 (1980).

    Article  CAS  Google Scholar 

  61. H. Tomioka, H. Okuno, and Y. Izawa, J. Org. Chem. 45, 5278 (1980)

    Article  CAS  Google Scholar 

  62. H. Tomioka, S. Suzuki, and Y. Izawa, J. Am. Chem. Soc. 104, 1047 (1982).

    Article  CAS  Google Scholar 

  63. H. Tomioka, S. Suzuki, and Y. Izawa, Bull. Chem. Soc. Jpn. 55, 492 (1982).

    Article  CAS  Google Scholar 

  64. H. Tomioka, N. Hayashi, Y. Izawa, V. P. Senthilnathan, and M. S. Platz, J. Am. Chem. Soc. 105, 5053 (1983);

    Article  CAS  Google Scholar 

  65. H. Tomioka, H. Ueda, S. Kondo, and Y. Izawa, J. Am. Chem. Soc. 102, 7817 (1980).

    Article  CAS  Google Scholar 

  66. E. C. Palik and M. S. Platz, J. Org. Chem. 48, 963 (1983).

    Article  CAS  Google Scholar 

  67. R. A. Moss and W. P. Wetter, Tetrahedron Lett. 22, 997 (1981).

    Article  CAS  Google Scholar 

  68. R. A. Barcus, E. C. Palik, and M. S. Platz, Tetrahedron Lett. 23, 1323 (1982).

    Article  CAS  Google Scholar 

  69. H. Tomioka, N. Hayashi, Y. Izawa, and M. T. H. Liu, Tetrahedron Lett. 25, 4413 (1984).

    Article  CAS  Google Scholar 

  70. R. J. McMahon and O. L. Chapman, J. Am. Chem. Soc. 109, 683 (1987);

    Article  CAS  Google Scholar 

  71. O. L. Chapman, J. W. Johnson, R. J. McMahon, and P. R. West, J. Am. Chem. Soc. 110, 501 (1988).

    Article  CAS  Google Scholar 

  72. G. G. Vander Stouw, A. R. Kraska, and H. Shechter, J. Am. Chem. Soc. 94, 1655 (1972)

    Article  Google Scholar 

  73. for reviews, see C. Wentrup, Top. Curr. Chem. 62, 173 (1976)

    Article  CAS  Google Scholar 

  74. P. P. Gaspar, J.-P. Hsu, S. Chari, and M. J. Jones, Tetrahedron 41, 1479 (1985).

    Article  CAS  Google Scholar 

  75. M. Platz, J. Am. Chem. Soc. 101, 3398 (1979).

    Article  CAS  Google Scholar 

  76. C. T. Lin and P. P. Gaspar, Tetrahedron Lett. 21, 3553 (1980).

    Article  CAS  Google Scholar 

  77. V. P. Senthilnathan and M. S. Platz, J. Am. Chem. Soc. 102, 7637 (1980);

    Article  CAS  Google Scholar 

  78. V. P. Senthilnathan and M. S. Platz, J. Am. Chem. Soc. 103, 5503 (1981);

    Article  CAS  Google Scholar 

  79. M. S. Platz, Acc. Chem. Res. 21, 236 (1988).

    Article  CAS  Google Scholar 

  80. Z. V. Bol’Shakov and V. A. Tolkatchev, Chem. Phys. Lett. 40, 468 (1976);

    Article  Google Scholar 

  81. Z. V. Bol’Shakov, M. P. Fuks, V. A. Tolkatchev, and A. I. Burstein, Radiat. Chem. 4, 723 (1976);

    Google Scholar 

  82. R. L. Hudson, M. Shiotan, and F. Williams, Chem. Phys. Lett. 48, 193 (1977).

    Article  CAS  Google Scholar 

  83. T. Doba, K. U. Ingold, W. Siebrand, and T. A. Wildman, Faraday Disc. Chem. Soc. 78, 175 (1984);

    Article  CAS  Google Scholar 

  84. T. Doba, K. U. Ingold, and W. Siebrand, Chem. Phys. Lett. 103, 339 (1983);

    Article  Google Scholar 

  85. T. Doba, K. U. Ingold, W. Siebrand, and T. A. Wildman, J. Phys. Chem. 88, 3163 (1984);

    Article  Google Scholar 

  86. T. Doba, K. U. Ingold, W. Siebrand, and T. A. Wildman, Chem. Phys. Lett. 115, 51 (1985)

    Article  CAS  Google Scholar 

  87. W. Siebrand and T. A. Wildman, Ace. Chem. Res. 19, 235 (1986).

    Google Scholar 

  88. J. M. Tedder, Tetrahedron 38, 313 (1982).

    Article  CAS  Google Scholar 

  89. J. Bigeleison, J. Phys. Chem. 56, 823 (1952).

    Article  Google Scholar 

  90. B. B. Wright, K. Kanakarajan, and M. S. Platz, J. Phys. Chem. 89, 3574 (1985).

    Article  CAS  Google Scholar 

  91. V. M. Maloney, Ph.D. thesis, The Ohio State University (1987).

    Google Scholar 

  92. R. P. Bell, The Tunnel Effect in Chemistry, Chapman and Hall, New York (1980).

    Book  Google Scholar 

  93. E. F. Caldin, Chem. Rev. 69, 135 (1969).

    Article  CAS  Google Scholar 

  94. R. J. LeRoy, H. Murai, and F. Williams, J. Am. Chem. Soc. 102, 2325 (1980).

    Article  CAS  Google Scholar 

  95. T. G. Savino, N. Soundararajan, and M. S. Platz, J. Phys. Chem. 90, 919 (1986).

    Article  CAS  Google Scholar 

  96. R. L. Barcus, B. B. Wright, E. Leyva, and M. S. Platz, J. Phys. Chem. 91, 6677 (1987).

    Article  CAS  Google Scholar 

  97. E. Leyva, unpublished research at The Ohio State University.

    Google Scholar 

  98. J. A. Ruzicka, M. Sc. thesis, The Ohio State University (1985).

    Google Scholar 

  99. A. Grimison and G. A. Simpson, J. Phys. Chem. 72, 1776 (1968).

    Article  CAS  Google Scholar 

  100. T. G. Savino, V. P. Senthilnathan, and M. S. Platz, Tetrahedron 42, 2167 (1986).

    Article  CAS  Google Scholar 

  101. I. Moritani, S. Murahashi, N. Nishino, K. Kimura, and H. Tsubomura, Tetrahedron Lett. 1966, 373;

    Google Scholar 

  102. I. Moritani, S. I. Murahashi, H. Ashitaka, K. Kimura, and H. Tsubomura, J. Am. Chem. Soc. 90, 5918 (1968).

    Article  CAS  Google Scholar 

  103. P. A. Gray, A. A. Herod, and A. Jones, Chem. Rev. 71, 257 (1971).

    Google Scholar 

  104. M. Shaffer, Ph.D. thesis, The Ohio State University (1987).

    Google Scholar 

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  1. Department of Chemistry, The Ohio State University, Columbus, Ohio, 43210-2251, USA

    Matthew S. Platz

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    Matthew S. Platz

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Platz, M.S. (1990). The Chemistry, Kinetics, and Mechanisms of Triplet Carbene Processes in Low-Temperature Glasses and Solids. In: Platz, M.S. (eds) Kinetics and Spectroscopy of Carbenes and Biradicals. Springer, Boston, MA. https://doi.org/10.1007/978-1-4899-3707-0_6

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