Advertisement

Electron Spin resonance Studies of Organotransition Metal Reactive Intermediates

  • Philip H. Rieger
Part of the NATO ASI Series book series (ASIC, volume 257)

Abstract

Electron spin resonance spectroscopy is a powerful tool for the study of organotransition metal radicals and radical ions. The technique can be used for the identification of radicals, measurement of radical concentrations, characterization of the molecular orbital containing the unpaired electron, and measurement of the rate of fluxionality in stereochemically nonrigid radicals. In this review, examples of ESR spectra of some simple radicals derived from manganese, iron, ruthenium, and cobalt carbonyls are discussed in the context of related electrochemical and chemical studies.

1987 marks the tenth anniversary of the first detailed study of the tricobalt carbon radical anions by Robinson, Simpson, and co-workers [1,2] and of my entry into the organometalic radical field as a sabbatical visitor at the University of Otago. I was not alone in my shift in research interests as several other ESR spectroscopists turned their attention in the same direction at about the same time, most notably Paul Krusic, Takashi Kawamura, John Morton, Keith Preston, and Martyn Symons. It seems appropriate to take the opportunity of a meeting devoted to the reactivities of organometallic radicals to review the role of ESR spectroscopy in the study of such species.

Keywords

Electron Spin Resonance Radical Anion Hyperfine Coupling Lewis Base Dalton Trans 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. [1]
    B. M. Peake, B. H. Robinson, J. Simpson, and D. J. Watson, Inorg. Chem. 1977, 16, 405.CrossRefGoogle Scholar
  2. [2]
    A.M. Bond, B. M. Peake, B. H. Robinson, J. Simpson, and D. J. Watson, Inorg. Chem. 1977, 16, 410.CrossRefGoogle Scholar
  3. [3]
    A.M. Peake, P. H. Rieger, B. H. Robinson, and J. Simpson, J. Am. Chem. Soc. 1980, 102, 156.CrossRefGoogle Scholar
  4. [4]
    W. E. Geiger, P. H. Rieger, B. Tulyathan, and M. D. Rausch, J. Am. Chem. Soc. 1984, 106, 7000.CrossRefGoogle Scholar
  5. [5]
    P. H. Rieger, J. Mag. Reson. 1982, 50, 485.Google Scholar
  6. J. A. DeGray and P. H. Rieger, Bull. Mag. Reson. 1987, 8, 95.Google Scholar
  7. [6]
    P. W. Atkins and M. C. R. Symons, The Structure of Inorganic Radicals, Amsterdam: Elsevier, 1967.Google Scholar
  8. [7]
    B. R. McGarvey, in Transition Metal Chemistry, Vol. 3, R. L. Carlin, ed, New York: Dekker, 1967.Google Scholar
  9. B. R. McGarvey, in Electron Spin Resonance of Metal Complexes, T. F. Yen, ed, New York: Plenum, 1969.Google Scholar
  10. [8]
    A.J. Stone, Proc. Roy. Soc. (London) 1963, A271, 424.Google Scholar
  11. [9]
    T. Kawamura, S. Hayashida, and T. Yonezawa, Chem. Phys. Lett. 1981, 77, 348.CrossRefGoogle Scholar
  12. T. Sowa, T. Kawamura, T. Yamabe, and T. Yonezawa, J. Am. Chem. Soc. 1985, 107, 6471.CrossRefGoogle Scholar
  13. [10]
    R. Wilson and D. Kivelson, J. Chem. Phys. 1964, 44, 154.CrossRefGoogle Scholar
  14. [11]
    B. M. Peake, P. H. Rieger, B. H. Robinson, and J. Simpson, Inorg. Chem. 1979, 18, 1000.CrossRefGoogle Scholar
  15. [12]
    T.-T. Chang, Mag. Reson. Rev. 1984, 9, 65.Google Scholar
  16. [13]
    R. D. Allendoerfer, G. A. Martinchek, and S. Bruckenstein, Anal. Chem. 1975, 47, 890.CrossRefGoogle Scholar
  17. [14]
    K. R. Fernando, A. J. McQuillan, B. M. Peake, and J. Wells, J. Magn. Reson. 1986, 68, 551.Google Scholar
  18. [15]
    G. J. Bezems, P. H. Rieger, and S. J. Visco, J. Chem. Soc., Chem. Commun. 1981, 265.Google Scholar
  19. [16]
    J. Grobe and H. Zimmermann, Z. Naturforsch. 1981, 36b, 301, 482.Google Scholar
  20. [17]
    D. P. Summers, J. C. Luong, and M. S. Wrighton, J. Am. Chem. Soc. 1981, 103, 5238.CrossRefGoogle Scholar
  21. [18]
    J. F. Bunnett, Accts. Chem. Res. 1978, 11, 413.CrossRefGoogle Scholar
  22. [19]
    I.P.Beletskaya and V. N. Drozd, Russ. Chem. Rev. 1979, 48, 431.CrossRefGoogle Scholar
  23. [20]
    R. W. Alder, J. Chem. Soc., Chem. Commun. 1980, 1184.Google Scholar
  24. [21]
    M. Saveant, Accts. Chem. Res. 1980, 13, 323.CrossRefGoogle Scholar
  25. [22]
    M. Chanon and M. L. Tobe, Angew. Chem., Intl. Ed. 1982, 21, 1.Google Scholar
  26. [23]
    B. H. Byers and T. L. Brown, J. Am. Chem. Soc. 1977, 99, 2527.CrossRefGoogle Scholar
  27. T. L. Brown, Ann. N. Y. Acad. Sci. 1980, 333, 80.CrossRefGoogle Scholar
  28. [24]
    J.K. Kochi, J. Organomet. Chem. 1986, 300, 139.CrossRefGoogle Scholar
  29. [25]
    M.I. Bruce, D. C. Kehoe, J. G. Matisons, B. K. Nicholson, P. H. Rieger, and M. L. Williams, J. Chem. Soc., Chem. Commun. 1982, 442.Google Scholar
  30. [26]
    H. H. Ohst and J. K. Kochi, J. Am. Chem. Soc. 1986, 108, 2897; Inorg. Chem. 1986 25, 2066.CrossRefGoogle Scholar
  31. [27]
    A. Darchen, C. Mahe, and H. Patin, J. Chem. Soc., Chem. Commun. 1982, 243.Google Scholar
  32. [28]
    M.I. Bruce, T. W. Hambley, B. K. Nicholson, and M. R. Snow, J. Organomet. Chem. 1982, 235, 83.CrossRefGoogle Scholar
  33. [29]
    I. Bruce, J. G. Matisons, B. K. Nicholson, and M. L. Williams, J. Organomet. Chem. 1982, 236, C57.CrossRefGoogle Scholar
  34. [30]
    M. I. Bruce, J. G. Matisons, and B. K. Nicholson, J. Organomet. Chem. 1983, 247, 321.CrossRefGoogle Scholar
  35. [31]
    J. Downard, B. H. Robinson, and J. Simpson, Organometallics 1986, 5, 1122, 1132.CrossRefGoogle Scholar
  36. [32]
    M. Arewgoda, B. H. Robinson, and J. Simpson, J. Am. Chem. Soc. 1983, 105, 1893.CrossRefGoogle Scholar
  37. [33]
    R. B. Cunninghame, L. R. Hanton, S. D. Jensen, B. H. Robinson, and J. Simpson, Organometallics 1987, 6, 1470.CrossRefGoogle Scholar
  38. S. D. Jensen, B. H. Robinson, and J. Simpson, ibid 1987, 6, 1479.Google Scholar
  39. [34]
    J. C. Kotz, J. V. Petersen, and R. C. Reed, J. Organomet. Chem. 1976, 120, 433.CrossRefGoogle Scholar
  40. [35]
    E. S. Lee and P. H. Rieger, unpublished work.Google Scholar
  41. [36]
    H. Beurich, T. Madach, R. Richter, and H. Vahrenkamp, Angew. Chem. 1979, 91, 760.CrossRefGoogle Scholar
  42. U. Honrath. L. Shu-Tang, and H. Vahrenkamp, Chem. Ber. 1985, 118, 132.CrossRefGoogle Scholar
  43. [37]
    J. A. Christie, D. N. Duffy, K. M. MacKay, and B. K. Nicholson, J. Organomet. Chem. 1982, 226, 165.CrossRefGoogle Scholar
  44. [38]
    N. Lindsay, B. M. Peake, B. H. Robinson, J. Simpson, U. Honrath, H. Vahrenkamp, and A. M. Bond, Organometallics 1984, 3, 413.CrossRefGoogle Scholar
  45. [39]
    B. M. Peake, P. H. Rieger, B. H. Robinson, and J. Simpson, Inorg. Chem. 1981, 20, 2540.CrossRefGoogle Scholar
  46. [40]
    C. E. Strouse and L. F. Dahl, Disc. Faraday Soc. 1969, 47, 93CrossRefGoogle Scholar
  47. C. E. Strouse and L. F. Dahl, J. Am. Chem. Soc. 1971, 93, 6032.CrossRefGoogle Scholar
  48. [41]
    R. S. Dickson, B. M. Peake, P. H. Rieger, B. H. Robinson, and J. Simpson, J. Organomet. Chem. 1979, 172, C63.CrossRefGoogle Scholar
  49. [42]
    M. Arewgoda, P. H. Rieger, B. H. Robinson, J. Simpson, and S. J. Visco, J. Am. Chem. Soc. 1982, 104, 5633.CrossRefGoogle Scholar
  50. [43]
    L. V. Casagrande, T. Chen, P. H. Rieger, R. H. Robinson, J. Simpson, and S. J. Visco, Inorg. Chem. 1984, 23, 2019.CrossRefGoogle Scholar
  51. [44]
    J. A. DeGray, Q.-J. Meng, and P. H. Rieger, J. Chem. Soc., Faraday Trans. I, in press.Google Scholar
  52. [45]
    H. J. Keller and H. Wawersik, Z. Naturforsch. 1965, 20b, 938.Google Scholar
  53. [46]
    L. A. Hanlan, E. P. Kundig, B. R. McGarvey, and G. A. Ozin, J. Am. Chem. Soc. 1975, 97, 7054.CrossRefGoogle Scholar
  54. [47]
    S. A. Fieldhouse, B. W. Fulham, G. W. Neilson, and M. C. R. Symons, J. Chem. Soc., Dalton Trans. 1974, 567.Google Scholar
  55. [48]
    P J. Krusic, J. San Filippo, Jr., B. Hutchinson, R. L. Hance, and L. M. Daniels, J. Am. Chem. Soc. 1981, 103, 2129.CrossRefGoogle Scholar
  56. [49]
    D. Miholová, J. Klima, and A. A. Vlček, Inorg. Chim. Acta 1978, 27, L67.CrossRefGoogle Scholar
  57. [50]
    P A. Dawson, B. M. Peake, B. H. Robinson, and J. Simpson, Inorg. Chem. 1980, 19, 465.CrossRefGoogle Scholar
  58. [51]
    B. M. Peake, B. H. Robinson, J. Simpson, and D. J. Watson, J. Chem. Soc., Chem. Commun. 1974, 945.Google Scholar
  59. [52]
    J. P. Collman, R. G. Finke, P. L. Matlock, R. Wahren, R. G. Komoto, and J. L. Brau- man, J. Am. Chem. Soc. 1978, 100, 1119.CrossRefGoogle Scholar
  60. [53]
    B. M. Peake, M. C. R. Symons, and J. L. Wyatt, J. Chem. Soc., Dalton Trans. 1983, 1171.Google Scholar
  61. [54]
    P. Chini, J. Organomet. Chem. 1980, 200, 37.CrossRefGoogle Scholar
  62. [55]
    C. J. Pickett and D. Pletcher, J. Chem. Soc., Dalton Trans. 1975, 879.Google Scholar
  63. [56]
    A.M. Bond, P. A. Dawson, B. M. Peake, B. H. Robinson, and J. Simpson, Inorg. Chem. 1977, 16, 2199.CrossRefGoogle Scholar
  64. [57]
    N. El Murr and A. Chaloyard, Inorg. Chem. 1982, 21, 2206.CrossRefGoogle Scholar
  65. [58]
    C. Amatore and P. J. Krusic, private communication.Google Scholar
  66. [59]
    D. Miholová, J. Fiedler, and A. A. Vlček, J. Electroanal. Chem. 1983, 143, 195.CrossRefGoogle Scholar
  67. [60]
    R.C. Dunbar, J. P. Ennever, and J. P. Fackler, Jr., Inorg. Chem. 1973, 12, 2734.CrossRefGoogle Scholar
  68. [61]
    J. H. Richardson, L. M. Stephenson, and J. L. Brauman, J. Am. Chem. Soc. 1974, 96, 3671.CrossRefGoogle Scholar
  69. [62]
    S. A. Fairhurst, J. R. Morton, and K. F. Preston, J. Chem. Phys. 1982, 77, 5872.CrossRefGoogle Scholar
  70. [63]
    T Lionel, J. R. Morton, and K. F. Preston, J. Chem. Phys. 1982, 76, 234.CrossRefGoogle Scholar
  71. [64]
    S. A. Fairhurst, J. R. Morton, R. N. Perutz, and K. F. Preston, Organometallics 1984, 3, 1389.CrossRefGoogle Scholar
  72. [65]
    C. J. Pickett and D. Pletcher, J. Chem. Soc., Dalton Trans. 1976, 636.Google Scholar
  73. [66]
    N. G. Connelly and K. R. Somers, J. Organomet. Chem. 1976, 113, C39.CrossRefGoogle Scholar
  74. [67]
    P. K. Baker, N. G. Connelly, B. M. R. Jones, J. P. Maher, and K. R. Somers, J. Chem. Soc., Dalton Trans., 1980, 579.Google Scholar
  75. [68]
    R. N. Bagchi, A. M. Bond, C. L. Heggie, T. L. Henderson, E. Mocellin, and R. A. Seikel, Inorg. Chem. 1983, 22, 3007.CrossRefGoogle Scholar
  76. [69]
    M. J. Therien and W. C. Trogler, J. Am. Chem. Soc. 1986, 108, 3697.CrossRefGoogle Scholar
  77. [70]
    J. E. Cyr, J. A. DeGray, D. K. Gosser, E. S. Lee, and P. H. Rieger, Organometallics 1985, 4, 950.CrossRefGoogle Scholar
  78. [71]
    A.J. Downard, B. H. Robinson, J. Simpson, and A. M. Bond, J. Organomet. Chem. 1987, 320, 363.CrossRefGoogle Scholar
  79. [72]
    J. E. Cyr and P. H. Rieger, to be published.Google Scholar
  80. [73]
    M. C. Manning and W. C. Trogler, Coord. Chem. Rev. 1981, 38, 89.CrossRefGoogle Scholar
  81. [74]
    P. Lemoine, A. Giraudeau, and M. Gross, Electrochim. Acta 1976, 21, 1.CrossRefGoogle Scholar
  82. [75]
    D. A. Lacombe, J. E. Anderson, and K. M. Kadish, Inorg. Chem. 1986, 25, 2074.CrossRefGoogle Scholar
  83. [76]
    Vlček, Jr. J. Organomet. Chem. 1986, 306, 63.CrossRefGoogle Scholar
  84. [77]
    A. Alberti, M. C. Depew, A. Hudson, W. G. McGimpsey, and J. K. S. Wan, J. Organomet. Chem. 1985, 280, C21.CrossRefGoogle Scholar
  85. [78]
    G. A. Abakumov, V. K. Cherkasov, K. G. Shalnova, I. A. Teplova, and G. A. Razu- vaev, J. Organomet. Chem. 1982, 236, 333.CrossRefGoogle Scholar
  86. [79]
    A. Alberti and C. M. Camaggi, J. Organomet. Chem. 1980, 194, 343.CrossRefGoogle Scholar
  87. [80]
    L. Pasimeni, P. L. Zanonato, and C. Corvaja, Inorg. Chim. Acta 1979, 37, 241.CrossRefGoogle Scholar
  88. [81]
    A.S. Huffadine, B M. Peake, B. M. Robinson, J. Simpson, and P. A. Dawson, J. Organomet. Chem. 1976, 121, 391.CrossRefGoogle Scholar
  89. [82]
    A. Hudson, M. G. Lappert, P. W. Lednor, and B. K. Nicholson, J. Chem. Soc., Chem. Commun. 1974, 966.Google Scholar
  90. [83]
    S. A. Hallock and A. Wojcicki, J. Organomet. Chem. 1973, 54, C27.CrossRefGoogle Scholar
  91. [84]
    C. L. Kwan and J. K. Kochi, J. Organomet. Chem. 1975, 101, C9.CrossRefGoogle Scholar
  92. [85]
    A. Hudson, M. F. Lappert, and B. K. Nicholson, J. Organomet. Chem 1975, 92, Cll.CrossRefGoogle Scholar
  93. [86]
    A. Hudson, M. F. Lappert, J. J. MacQuitty, B. K. Nicholson, H. Zainal, G. R. Luckhurst, C. Zannoni, S. W. Bratt, and M. C. R. Symons, J. Organomet. Chem. 1976, 110, C5.CrossRefGoogle Scholar
  94. [87]
    J. A. Howard, J. R. Morton, and K. F. Preston, Chem. Phys. Lett. 1981, 83, 226.CrossRefGoogle Scholar
  95. [88]
    H. Huber, E. P. Kündig, G. A. Ozin, and A. J. Poë, J. Am. Chem. Soc. 1985, 97, 308. ESR result quoted by Huffadine, et al. [81].CrossRefGoogle Scholar
  96. [89]
    M. C. R. Symons and R. L. Sweany, Organometallics 1982, 1, 834.CrossRefGoogle Scholar
  97. [90]
    S. P. Church, M. Poliakoff, J. A. Timney, and J. J. Turner, J. Am. Chem. Soc. 1981, 103, 7515.CrossRefGoogle Scholar
  98. [91]
    W. K. Meckstroth and D. P. Ridge, J. Am. Chem. Soc. 1985, 107, 2281.CrossRefGoogle Scholar
  99. [92]
    O. P. Anderson and M. C. R. Symons, J. Chem. Soc., Chem. Commun. 1972, 1020.Google Scholar
  100. [93]
    S. W. Bratt and M. C. R. Symons, J. Chem. Soc., Dalton Trans. 1977, 1314.Google Scholar
  101. [94]
    T. Lionel, J. R. Morton, and K. F. Preston, Inorg. Chem. 1983, 22, 143.CrossRefGoogle Scholar
  102. [95]
    M. C. R. Symons, J. Wyatt, B. M. Peake, J. Simpson, and B. H. Robinson, J. Chem. Soc., Dalton Trans. 1982, 2037.Google Scholar
  103. [96]
    G. R. Lemke and C. P. Kubiak, Inorg. Chim. Acta 1986, 113, 125.CrossRefGoogle Scholar

Copyright information

© Kluwer Academic Publishers 1989

Authors and Affiliations

  • Philip H. Rieger
    • 1
  1. 1.Department of ChemistryBrown UniversityProvidenceUSA

Personalised recommendations