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Chemical Kinetics and Inorganic Reaction Mechanisms pp 261–279Cite as

Metallocenes, Strong Electron Donors

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Abstract

For many years it was puzzling that metal atoms, which were not considered good Lewis acids, could form adducts with CO, considered to be a poor donor toward most Lewis acids. An example is the hexacarbonylchromium, Cr(CO)6. On the other hand, it was stressed that chromium, having 24 electrons, by accepting 6x2 electrons from 6 CO molecules, will fill its orbitals to a total of 36 electrons, which is the electron configuration of krypton. The LCAO approximation method (linear combination of atomic orbitals) helped to explain the stability of these adducts as being due to a two-way acid-base interaction between the metal and CO: the metal synergically interacts with CO, acting as an acid and a base, while CO simultaneously behaves as a donor and acceptor. In 1955 Ernst Otto Fischer, University of Munich, showed that an increase of the number of chromium electrons to 36 can be achieved by three π-electron pairs of benzene, like, e.g., in benzenetricarbonylchromium, (C6H6)Cr(CO)3. Cyclopentadienyl, C5H5 -, has also been known to form compounds with metal atoms.

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References

  1. T. J. Kealy and P. L. Pauson, Nature, 1951, 168, 1039.

    Article  CAS  Google Scholar 

  2. M. Rosenblum, Chemistry of the Iron Group Metallocenes, Interscience, New York 1965.

    Google Scholar 

  3. G. Wilkinson, J. Organomet. Chem. 1975, 100, 273.

    Article  CAS  Google Scholar 

  4. J. S. Thayer, Adv. Organomet. Chem. 1975, 13, 1.

    Article  CAS  Google Scholar 

  5. K. F. Purcell and J. C. Kotz, Inorganic Chemistry, W. B.Saunders, Philadelphia 1977, p. 877.

    Google Scholar 

  6. C. A. Tolman, Chem. Soc. Rev.Chem. Soc. Rev. 1972,1, 337.

    Article  CAS  Google Scholar 

  7. F. A. Cotton, J. Organomet. Chem. 1975, 100, 29.

    Google Scholar 

  8. M. Green, D. M. Grove, J. A. K. Howard, J. L. Spencer, and F. G. A. Stone, J. Chem. Soc, Chem. Commun. 19761976, 759.

    Article  Google Scholar 

  9. Ref. 4, pp. 1-49.

    Google Scholar 

  10. F. A. Cotton and G. Wilkinson, Advanced Inorganic Chemistry, 5th ed., Wiley, New York 1988, pp. 78–83.

    Google Scholar 

  11. J. Howard, J. Chem. Soc, Dalton Trans. 1982, 967.

    Google Scholar 

  12. R. K. Bohn and A. Haaland, J. Organomet. Chem. 1966, 5, 470.

    Article  CAS  Google Scholar 

  13. G. J. Palenik, Inorg. Chem. 1970, 9, 2424.

    Article  CAS  Google Scholar 

  14. R. L. Sime and R. J. Sime, J. Am. Chem. Soc. 1974, 96, 892.

    Article  CAS  Google Scholar 

  15. M. Cais, Organomet. Chem. Rev. 1966, 1, 435.

    CAS  Google Scholar 

  16. T. G. Traylor and J. C. Ware, J. Am. Chem. Soc. 1967, 89, 2304.

    Article  CAS  Google Scholar 

  17. T. D. Turbitt and W. E. Watts, J. Chem. Soc, Perkin Trans. 2, 1974, 177, and refs. therein.

    Google Scholar 

  18. J. W. Larsen and P. Ashkenazi, J. Am. Chem. Soc. 1975, 97, 2140.

    Article  CAS  Google Scholar 

  19. C. C. Lee, S. C. Chen, W J. Pannekoek, and R. G. Sutherland, J. Organomet. Chem. 1976, 118, C47.

    Article  CAS  Google Scholar 

  20. M. Hisatome and K. Yamakawa, J. Organomet. Chem. 1977, 133, C9.

    Article  CAS  Google Scholar 

  21. W.E. Watts, J. Chem. Soc, Perkin Trans. 1976, 1, 804.

    Article  Google Scholar 

  22. S. Ursic and S. Ašperger, J. Inorg. Nucl. Chem. 1979, 41, 1329, and refs. therein.

    Article  CAS  Google Scholar 

  23. R. Gleiter and R. Seeger, Helv. Chim. Acta, 1971, 54, 1217.

    Article  CAS  Google Scholar 

  24. M. J. Nugent, R. E. Carter, and J. H. Richards, J. Am. Chem. Soc 1969, 91, 6145.

    Article  CAS  Google Scholar 

  25. M. Cais, J. J. Dannenberg, A. Eisenstadt, M. L. Levenberg, and J. H. Richards, Tetrahedron Lett. 1966, 1695.

    Google Scholar 

  26. M. Hisatome and K. Yamakawa, Tetrahedron Lett. 1971, 27, 2101; ibid, 3533.

    CAS  Google Scholar 

  27. J. J. Dannenberg, M. L. Levenberg, and J. H. Richards, Tetrahedron, 1973, 29, 1575.

    Article  CAS  Google Scholar 

  28. A. Streitwieser, Jr., and R. C. Fahey, Chem. Ind. (London) 1957, 1417.

    Google Scholar 

  29. W. H. Saunders, Jr., S. Ašperger, and D. H. Edison, Chem. Ind. (London), 1957, 1417.

    Google Scholar 

  30. A. Streitwieser, Jr., R. H. Jagow, R. C. Fahey, and S. Suzuki, J. Am. Chem. Soc. 1958, 80, 2326.

    Article  CAS  Google Scholar 

  31. W. H. Saunders, Jr., S. Ašperger, and D. H. Edison, J. Am. Chem. Soc 1958, 80, 2421.

    Article  CAS  Google Scholar 

  32. K. Mislow, S. Borcic, and V. Prelog, Helv. Chim. Acta, 1957, 40, 2477.

    Article  CAS  Google Scholar 

  33. R. R. Johnson and E. S. Lewis, Proc. Chem. Soc 1958, 52.

    Google Scholar 

  34. D. E. Sunko and S. Borcic, ACS Monogr. No. 167, Chap. 3; L. Melander and W H. Saunders, Jr., Reaction Rates of Isotopic Molecules, Wiley, New York 1980; A. Thibblin and P. Ahlberg, Chem. Soc. Rev. 1989, 18, 209-224.

    Google Scholar 

  35. D. E. Sunko, Croat. Chem. Acta, 1996, 69, 1275–1304.

    CAS  Google Scholar 

  36. K. C. Westway in: E. Buncel and C. C. Lee, Eds., Isotopes in Organic Chemistry, Vol. 7, Elsevier, Amsterdam 1987, Chap. 5.

    Google Scholar 

  37. B. Capon and S. P. Mc Manus. Neighboring Group Participation, Plenum Press, New York 1976.

    Book  Google Scholar 

  38. D. T. Stoelting and V. J. Shiner, Jr., J. Am. Chem. Soc. 1993, 115, 1695; V. J. Shiner and F. P. Wilgis, in: E. Buncel and W. H. Saunders Jr., Eds., Isotopes in Organic Chemistry, Vol. 8, Elsevier, Amsterdam 1992, Chap. 6; V. J. Shiner, Jr., T. E. Neumann, and B. B. Basinger, Croat Chem. Acta, 1996, 69, 1405.

    Article  CAS  Google Scholar 

  39. Y. Zhang, J. Bommuswamy, and M. L. Sinnott, J. Am. Chem. Soc. 1994, 116, 7557.

    Article  CAS  Google Scholar 

  40. S. Ašperger, D. Pavlović, Z. Kukrić, and D. Šutić, Inorg. Chim. Acta, 1990, 171, 5.

    Article  Google Scholar 

  41. V. J. Shiner, Jr., ACS Monogr. No. 167, 1970, p. 104.

    Google Scholar 

  42. A. Streitwieser, Jr. and G. A. Daffon, Tetrahedron Lett. 1969, 1263.

    Google Scholar 

  43. V. J. Shiner, Jr., M. W. Rapp, E. A. Halevi, and M. Wolfsberg, J. Am. Chem. Soc. 1968, 90, 7171.

    Article  CAS  Google Scholar 

  44. M. Schwarz, Ed., Ions and Ion Pairs in Organic Reactions, Vol. 2, Wiley, New York 1974, pp. 297–329.

    Google Scholar 

  45. B. Goričnik, Z. Majerski, S. Borčić, and D. E. Sunko, J. Org. Chem. 1973, 38, 1881.

    Article  Google Scholar 

  46. D. Šutić, S. Ašperger, and S. Borčić, Org. Chem. 1982, 47, 5120.

    Article  Google Scholar 

  47. E. A. Hill and J. H. Richards, J. Am. Chem. Soc. 1961, 83, 3840.

    Article  CAS  Google Scholar 

  48. S. Winstein and R. Heck, J. Am. Chem. Soc. 1956, 78, 4801.

    Article  CAS  Google Scholar 

  49. S. Winstein and G. C. Robinson, J. Am. Chem. Soc. 1958, 80, 169.

    Article  CAS  Google Scholar 

  50. S. Ašperger, Z. Kukrić, W. H. Saunders, Jr., and D. Šutić, J. Chem. Soc, Perkin. Trans. 2, 1992, 275.

    Google Scholar 

  51. S. R. Hartshorn and V. J. Shiner, Jr., J. Am. Chem. Soc. 1972, 94, 9002.

    Article  CAS  Google Scholar 

  52. E. G. Perevalova, Yu. A. Ustynyuk, and A. N. Nesmeyanov, Izv. Akad. Nauk SSSR, Otd. Khim. Nauk, 1963, 1036.

    Google Scholar 

  53. W. H. Saunders, Jr., J. Am. Chem. Soc. 1985, 107, 164.

    Article  CAS  Google Scholar 

  54. M. Amin, R. C. Price, and W. H. Saunders, Jr., J. Am. Chem. Soc. 1990, 112, 4467.

    Article  CAS  Google Scholar 

  55. L. Melander and W. H. Saunders, Jr., Reaction Rates of Isotopic Molecules, Wiley-Interscience, New York 1980, pp. 140–152.

    Google Scholar 

  56. S. Winstein and G. C. Robinson, J. Am. Chem. Soc. 1958, 80, 169.

    Article  CAS  Google Scholar 

  57. C. A. Bunton, N. Carrasco, F. Davoudzadeh, and W. E. Watts, J. Chem. Soc, Perkin Trans 2, 1980, 1520.

    Google Scholar 

  58. J. H. Richards and E. A. Hill, J. Am. Chem. Soc. 1959, 81, 3484.

    Article  CAS  Google Scholar 

  59. G. Gerichelli, B. Floris, and G. Ortaggi, J. Organomet. Chem. 1974, 78, 241.

    Article  Google Scholar 

  60. C. Lo Sterzo and G. Ortaggi, Tetrahedron, 1984, 40, 593.

    Article  Google Scholar 

  61. C. A. Bunton, N. Carrasco, and W. E. Watts, J. Organomet. Chem., C, 1977, 131, 21.

    Article  Google Scholar 

  62. L. I. Kazakova, N. M. Loim, E. G. Perevalova, and Z. N. Parnes, J. Org. Chem. USSR (Engl. Transl.), 1974, 2294.

    Google Scholar 

  63. C. A. Bunton, W. E. Watts, Tetrahedron Lett. 1977, 2049.

    Google Scholar 

  64. C. A. Bunton, N. Carrasco, N. Cully, and W. E. Watts, J. Chem. Soc, Perkin Trans. 2, 1980, 1859.

    Google Scholar 

  65. H. Mayr and D. Rau, Chem. Ber. 1994, 127, 2493.

    Article  CAS  Google Scholar 

  66. G. Neshvad, R. M. G. Roberts, and J. Silver, J. Organomet. Chem. 1982, 236, 237.

    Article  CAS  Google Scholar 

  67. C. Cordier, M. Gruselle, J. Vaissermann, L. L. Troitskaya, V. I. Bakhmutov, V. I. Sokolov, and G. Jauoen, Organometallics, 1992, 11, 3825.

    Article  CAS  Google Scholar 

  68. S. Braun, T. S. Abram, and W E. Watts, J. Organomet. Chem. 1975, 97, 429.

    Article  CAS  Google Scholar 

  69. U. Behrens, J. Organomet. Chem. 1979, 182, 89.

    Article  CAS  Google Scholar 

  70. G. A. Olah, P. W. Westerman, and D. A. Forsyth, J. Am. Chem. Soc. 1975, 97, 3419.

    Article  CAS  Google Scholar 

  71. K. V. Kilway and A. Streitwieser, Jr., Abstracts of 213 ACS National Meeting, San Francisco, CA, April 13-17, 1997.

    Google Scholar 

  72. C. A. Bunton and A. Konasiewicz, J. Chem. Soc. 1955, 1354.

    Google Scholar 

  73. C. G. Swain, R. B. Mosely, and D. F. Bown, J. Am. Chem. Soc. 1955, 77, 3731; C. G. Swain, T. E. C. Knee, and A. Maclachlan, J. Am. Chem. Soc. 1960, 82, 6101.

    Article  CAS  Google Scholar 

  74. D. N. Kevill and A. R. Pinhas, J. Org. Chem. 1993, 58, 197.

    Article  CAS  Google Scholar 

  75. S. Winstein, B. Appel, R. Baker, and A. Diaz, in: Organic Reaction Mechanisms, The Chemical Society, London 1965, pp. 124–126.

    Google Scholar 

  76. A. H. Fainberg and S. Winstein, J. Am. Chem. Soc. 1956, 78, 2770.

    Article  CAS  Google Scholar 

  77. T. W. Bentley and P.v. R. Schleyer, J. Am. Chem. Soc. 1976, 98, 7658.

    Article  CAS  Google Scholar 

  78. S. Winstein, E. Grunwald, and L. L. Ingraham, J. Am. Chem. Soc. 1948, 70, 821.

    Article  CAS  Google Scholar 

  79. S. Ašperger and B. Cetina-Čižmek, in preparation.

    Google Scholar 

  80. D. N. Kevill and S. W. Abderson, J. Am. Chem. Soc. 1986, 108, 1579.

    Article  CAS  Google Scholar 

  81. R. S. Drago and D. C. Ferris, J. Phys. Chem. 1995, 99, 6563.

    Article  CAS  Google Scholar 

  82. M. J. Weaver, Chem. Rev. 1992, 92, 463, and refs. therein.

    Article  CAS  Google Scholar 

  83. G. E. Mc Mannis, R. M. Nielson, A. Gochev, and M. J. Weaver, J. Am. Chem. Soc. 1989, 111, 5533.

    Article  Google Scholar 

  84. R. M. Nielson, G. E. Mc Manis, M. N. Golovin, and M. J. Weaver, J. Phys. Chem. 1988, 92, 3441.

    Article  CAS  Google Scholar 

  85. H. Köpf, Anticancer Res. 1986, 6, 33; Arzneim. Forsch. 1987, 37, 532; Eur. J. Cancer Clin. Oncol. 1985, 21, 853.

    Google Scholar 

  86. N. Freestone, Educ. Chem. 1988, 25, 156.

    Google Scholar 

  87. S. E. Sherman and S. J. Lippard, Chem. Rev. 1987, 1153.

    Google Scholar 

  88. A. Pasini and F. Zunino, Angew. Chem., Int. Ed. Engl. 1987, 26, 615.

    Article  Google Scholar 

  89. M. J. S. Dewar and K. M. Merz, J. Am. Chem. Soc. 1987, 109, 6553.

    Article  CAS  Google Scholar 

  90. B. K. Keppler and K. Michels, Arzneim. Forsch. 1985, 35, 1837.

    CAS  Google Scholar 

  91. P. Köpf-Maier and H. Köpf, Chem. Rev. 1987, 87, 1137.

    Article  Google Scholar 

  92. I. Haiduc and C. Silvestru, Coord. Chem. Rev. 1990, 99, 253–296.

    Article  CAS  Google Scholar 

  93. J. C. Ruble and G. C. Fu, J. Org. Chem. 1996, 61, 7230.

    Article  CAS  Google Scholar 

  94. E. F. V. Scriven, Chem. Soc. Rev. 1983, 12, 129.

    Article  CAS  Google Scholar 

  95. E. Vedejs and X. Chen, J. Am. Chem. Soc. 1996, 118, 1809.

    Article  CAS  Google Scholar 

  96. J. C. Ruble, H. A. Latham, and G. C. Fu, J. Am. Chem. Soc. 1997, 119, 1492.

    Article  CAS  Google Scholar 

  97. S. Stinson, Chem. Eng. News, 1997 (February 17), p. 10.

    Google Scholar 

  98. A. Togni and T. Hayashi, Eds., Ferrocenes, VCH, New York 1995.

    Google Scholar 

  99. A. Togni, Angew. Chem., Int. Ed. Engl. 1996, 35, 1475.

    Article  CAS  Google Scholar 

  100. H. C. L. Abbenhuis, U. Burckhardt, V. Gramlich, A. Martelletti, J. Spencer, I. Steiner, and A. Togni, Organometallics, 1996, 15, 1614.

    Article  CAS  Google Scholar 

  101. C. Janiak and H. Schumann, Adv. Organomet. Chem. 1991, 33, 291.

    Article  CAS  Google Scholar 

  102. C. J. Pederson, J. Am. Chem. Soc. 1967, 89, 2495.

    Article  Google Scholar 

  103. J. C. Medina, I. Gay, Z. Chen, L. Echegoyen, and G. W. Gokel, J. Am. Chem. Soc. 1991, 113, 365.

    Article  CAS  Google Scholar 

  104. J. C. Medina, C. Li, S. G. Bott, J. L. Atwood, and G. W. Gokel, J. Am. Chem. Soc. 1991, 113, 366.

    Article  CAS  Google Scholar 

  105. E. C. Constable, Angew. Chem., Int. Ed. Engl. 1991, 30, 407.

    Article  Google Scholar 

  106. J. C. Medina, T. T. Goodnow, M. T. Rojas, J. L. Atwood, B. C. Lynn, E. A. Kaifer, and G. W. Gokel, J. Am. Chem. Soc. 1992, 114, 10583.

    Article  CAS  Google Scholar 

  107. P. D. Beer, Z. Chen, M. G. B. Drew, J. Kingston, M. Ogden, and P. Spencer, J. Chem. Soc, Chem. Commun. 1993, 1046, and refs. therein.

    Google Scholar 

  108. Z. Chen, A. R. Graydon, and P. D. Beer, J. Chem. Soc, Faraday Trans. 2, 1996, 97.

    Article  Google Scholar 

  109. B. Dietrich, Pure Appl. Chem. 1993, 65, 1457.

    Article  CAS  Google Scholar 

  110. P. D. Beer, Z. Chen, A. J. Goulden, A Grieve, D. Hesek, F. Szemes, and T. Wear, J. Chem. Soc, Chem. Commun. 1994, 1269; P. D. Beer, D. Hesek, J. Hadacovd, and S. E. Stokes, J. Chem. Soc, Chem. Commun. 1992, 270; P. D. Beer, Chem. Soc. Rev. 1989,18, 409.

    Google Scholar 

  111. S. Barlow and D. O’Hare, Chem. Rev. 1997, 97, 637–669.

    Article  CAS  Google Scholar 

  112. H. H. Brintzinger, D. Fischer, R. Mülhaupt, B. Rieger, and R. Waymouth, Angew. Chem. 1995, 107, 1255; Angew. Chem., Int. Ed. Engl. 1995, 34, 143; H. Cherdron, M. J. Brekner, and F. Osan, Angew. Macromol. Chem. 1994, 223, 121.

    Article  Google Scholar 

  113. W. A. Herrmann and B. Cornils, Angew. Chem., Int. Ed. Engl. 1997, 36, 1048–1067.

    Article  Google Scholar 

  114. P. Gómez-Elipe, P. M. Macdonald, and I. Manners, Angew. Chem., Int. Ed. Engl. 1997, 7, 762; I. Manners, Adv. Organomet. Chem. 1995, 37, 131; S. Barlow, L. Rohl, S. Shi, C. M. Freeman, and D. O’Hare, J. Am. Chem. Soc. 1996, 118, 7578; R. Rulkens, Y. Ni, and I. Manners, J. Am. Chem. Soc. 1994, 116, 12121; T. J. Peckham, J. A. Massey, M. Edwards, I. Manners, and D. A. Fencher, Macromolecules, 1996, 29, 2396.

    Article  Google Scholar 

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    Smiljko Ašperger (Professor of Chemistry)

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Ašperger, S. (2003). Metallocenes, Strong Electron Donors. In: Chemical Kinetics and Inorganic Reaction Mechanisms. Springer, Boston, MA. https://doi.org/10.1007/978-1-4419-9276-5_10

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