Skip to main content
SpringerLink
Log in

Organometallic Chemistry of Transition Metals

  • Chapter
  • First Online:
Principles of Inorganic Chemistry

  • 120 Accesses

Abstract

These compounds have at least one metal–carbon bond, but species with metal–phosphane bonds often are included in this family. The historical background is followed by descriptions of the bonding in terms of qualitative valence bond theory, molecular orbital theory, and the eighteen-electron rule. These approaches can rationalize the stability and arrangement of the ligands around the metal. The metal carbonyls and metal cyclopentadienes are important members of this family, and their bonding is described in detail. The syntheses and reactions of some representative organometallic species are described. The final section involves the use of organometallic species as catalysts for the homogeneous hydrogenation of organic substrates. The coverage of these topics includes references published through to mid-2021.

This is a preview of subscription content, log in via an institution to check access.

Access this chapter

Log in via an institution
Chapter
USD 29.95
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
eBook
USD 119.00
Price excludes VAT (USA)
  • Available as EPUB and PDF
  • Read on any device
  • Instant download
  • Own it forever
Hardcover Book
USD 159.99
Price excludes VAT (USA)
  • Durable hardcover edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info

Tax calculation will be finalised at checkout

Purchases are for personal use only

Institutional subscriptions

Notes

  1. 1.

    Spessard, G. O.; Miessler, G. L. Organometallic Chemistry, 3rd ed.; Oxford University Press: New York, 2015; Crabtree, R. H. The Organometallic Chemistry of the Transition Metals, 6th ed.; Wiley: New York, 2014; Elschenbroich, C. Organometallics, 3rd ed.; Wiley–VCH: Weinheim, 2006; Hartwig, J. Organotransition Metal Chemistry: From Bonding to Catalysis, University Science Books, 2009.

  2. 2.

    Thayer, J. S. J. Chem. Educ. 1969, 46, 442; Seyferth, D. Organometallics 2001, 20, 2.

  3. 3.

    Love, R. A.; Koetzle, T. F.; Williams, G. J. B.; Andrews, L. C.; Bau, R. Inorg. Chem. 1975, 14, 2653.

  4. 4.

    Thayer, J. S. J. Chem. Educ. 1969, 46, 764; Seyferth, D. Organometallics 2001, 20, 2940.

  5. 5.

    Seyferth, D. Organometallics 2003, 22, 2346; Ibid., 5154.

  6. 6.

    Mond, L.; Langer, C.; Quincke, F. J. Chem. Soc. Trans. 1890, 57, 749.

  7. 7.

    Mond, L.; Langer, C. J. Chem. Soc. Trans. 1891, 59, 1090.

  8. 8.

    Dewar, J.; Jones, H. O. Proc. R. Soc. London Ser. A 1907, 78, 66.

  9. 9.

    Farrugia, L. J.; Evans, C. J. Phys. Chem. A 2005, 109, 8834.

  10. 10.

    Cotton, F. A.; Troup, J. M. J. Chem. Soc. Dalton 1974, 800.

  11. 11.

    Kealy, T. J.; Pauson, P. L. Nature 1951, 168, 1039; Miller, S. A.; Tebboth, J. A.; Tremaine, J. F. J. Chem. Soc. 1952, 632.

  12. 12.

    Werner, H. Angew. Chem., Int. Ed. 2012, 51, 6052; Okuda, J. Eur. J. Inorg. Chem. 2017, 217.

  13. 13.

    Eiland, P. F.; Pepinsky, R. J. Am. Chem. Soc. 1952, 74, 4971; Dunitz, J. D.; Orgel, L. E. Nature 1953, 171, 121.

  14. 14.

    Appel, M.; Frick, B.; Spehr, T. L.; Stühn, B. J. Chem. Phys. 2015, 142, #114503, and references therein.

  15. 15.

    Haaland, A. Acct. Chem. Res. 1979, 12, 415, and references therein.

  16. 16.

    Seiler, P.; Dunitz, J. D. Acta Crystallogr. B 1982, 38, 1741.

  17. 17.

    Brock, C. P.; Fu, Y. Acta Crystallogr. B 1997, 53, 928, and references therein.

  18. 18.

    Astruc, D. Eur. J. Inorg. Chem. 2017, 6.

  19. 19.

    Fischer, E. O.; Hafner, W. Z. Naturforsch. B 1955, 10, 665; Ibid Z. Anorg. Allg. Chem. 1956, 286, 146.

  20. 20.

    Weiss, E.; Fischer, E. O. Z. Anorg. Allg. Chem. 1956, 286, 142.

  21. 21.

    Seyferth, D. Organometallics 2002, 21, 2800; Fischer, R.; Görls, H.; Suxdorf, R.; Westerhausen, M. Organometallics 2019, 38, 498; Ibid 2020, 39, 3892.

  22. 22.

    Lyssenko, K. A.; Korlyukov, A. A.; Golovanov, D. G.; Ketkov, S. Y.; Antipin, M. Y. J. Phys. Chem. A 2006, 110, 6545.

  23. 23.

    Hopkinson, M. N.; Richter, C.; Schedler, M.; Glorius, F. Nature 2014, 510, 485; Hahn, F. E.; Jahnke, M. C. Angew. Chem., Int. Ed. 2008, 47, 3122; Paul, U. S. D.; Radius, U. Eur. J. Inorg. Chem. 2017, 3362; Huynh, H. V. Chem. Rev. 2018, 118, 9457; Khan, S.; Roesky, H. W. Chem. Eur. J. 2019, 25, 1636; Reshi, N. U. D; Bera, J. K. Coord. Chem. Rev. 2020, 422, #213334.

  24. 24.

    Arduengo, A. J., III; Harlow, R. L.; Kline, M. J. Am. Chem. Soc. 1991, 113, 361.

  25. 25.

    Sundberg, R. J.; Bryan, R. F.; Taylor, I. F., Jr.; Taube, H. J. Am. Chem. Soc. 1974, 96, 381.

  26. 26.

    Walter, M. D.; Baabe, D.; Freytag, M.; Jones, P. G. Z. Anorg. Allg. Chem. 2016, 642, 1259.

  27. 27.

    Burling, S.; Mahon, M. F.; Powell, R. E.; Whittlesey, M. K.; Williams, J. M. J. J. Am. Chem. Soc. 2006, 128, 13702.

  28. 28.

    Langmuir, I. Science 1921, 54, 59; Sidgwick, N. V. Trans. Faraday Soc. 1923, 19, 469; Sidgwick, N. V.; Bailey, R. W. Proc. Royal Soc. London A 1934, 144, 521.

  29. 29.

    Bellard, S.; Rubinson, K. A.; Sheldrick, G. M. Acta Crystallogr. B 1979, 35, 271.

  30. 30.

    Farrugia, L. J.; Mallinson, P. R.; Stewart, B. Acta Crystallogr. B 2003, 59, 234.

  31. 31.

    Garcia, T. Y.; Fettinger, J. C.; Olmstead, M. M.; Balch, A. L. Chem. Commun. 2009, 7143.

  32. 32.

    Leung, P. C.; Coppens, P. Acta Crystallogr. B 1983, 39, 535.

  33. 33.

    Ponec, R. Compt. Theor. Chem. 2015, 1053, 195, and references therein; Green, M. L. H.; Parkin, G. Stuct. Bond. 2017, 171, 79, and references therein.

  34. 34.

    Foroutan-Nejad, C.; Shahbazian, S.; Marek, R. Chem. Eur. J. 2014, 20, 10140, and references therein.

  35. 35.

    Van der Maelen, J. F.; C abeza, J. A. Theor. Chem. Acc. 2016, 135, #64.

  36. 36.

    Joy, J.; Danovich, D.; Kaupp, M.; Shaik, S. J. Am. Chem. Soc. 2020, 142, 12277.

  37. 37.

    Pan, S.; Zhao, L.; Dias, H. V. R.; Frenking, G. Inorg. Chem. 2018, 57, 7780.

  38. 38.

    Campana, C. F.; Guzei, I. A.; Mednikov, E. G.; Dahl, L. F. J. Clust. Sci. 2014, 25, 205.

  39. 39.

    Churchill, M. R.; DeBoer, B. Inorg. Chem. 1977, 16, 878.

  40. 40.

    Landis C. R.; Weinhold, F. J. Comput. Chem. 2007, 28, 198; Ibid 2016, 37, 237.

  41. 41.

    Bachler, V. J. Comput. Chem. 2012, 33, 1936.

  42. 42.

    Diefenbach, A.; Bickelhaupt, F. M.; Frenking, G. J. Am. Chem. Soc. 2000, 122, 6449.

  43. 43.

    Drouin, B. J.; Kukolich, S. G. J. Am. Chem. Soc. 1999, 121, 4023.

  44. 44.

    Karunatilaka, C.; Tackett, B. S.; Washington, J.; Kukolich, S. G. J. Am. Chem. Soc. 2007, 129, 10522.

  45. 45.

    Bennett, M. J.; Donaldson, P. B, Inorg. Chem. 1977, 16, 655.

  46. 46.

    Olsen, E. P. K.; Singh, T.; Harris, P.; Andersson, P. G.; Madsen, R. J. Am. Chem. Soc. 2015, 137, 834.

  47. 47.

    Goodman, J.; Grushin, V. V.; Larichev, R. B.; Macgregor, S. A.; Marshall, W. J.; Roe, D. C. J. Am. Chem. Soc. 2010, 132, 12013.

  48. 48.

    Rheingold, A. L.; Geib, S. J. Acta Crystallogr. C 1987, 43, 784; Chen, Y.-J.; Wang, J.-C.; Wang, Y. Ibid, 1991, 47, 2441.

  49. 49.

    Harlow, R. L.; Westcott, S. A.; Thorn, D. L.; Baker, R. T. Inorg. Chem. 1992, 31, 323.

  50. 50.

    Cassidy, J. M.; Whitmire, K. H. Acta Crystallogr. C 1991, 47, 2094.

  51. 51.

    Jones, R. A.; Stuart, A. L.; Atwood, J. L.; Hunter, W. E. J. Crystallogr. Spect. Res. 1983, 13, 273.

  52. 52.

    Krzystek, J.; Ozarowski, A.; Zvyagin, S. A.; Telser, J. Inorg. Chem. 2012, 51, 4954.

  53. 53.

    Willner, H.; Aubke, F. Angew. Chem., Int. Ed. 1997, 36, 2402, and references therein.

  54. 54.

    Martínez-Salvador, S.; Forniés, J.; Martín, A.; Menjón, B. Angew. Chem., Int. Ed. 2011, 50, 6571.

  55. 55.

    Dewar, M. J. S. Bull. Soc. Chim. Fr. 1951, 18, C71; Chatt, J.; Duncanson, L. A. J. Chem. Soc. 1953, 2939.

  56. 56.

    Bistoni, G.; Rampino, S.; Scafuri, N.; Ciancaleoni, G.; Zuccaccia, D.; Belpassi, L.; Tarantelli, F. Chem. Sci. 2016, 7, 1174.

  57. 57.

    Van Resensburg, H.; Tooze, R. P.; Foster, D. F.; Otto, S. Inorg. Chem. 2007, 46, 1963.

  58. 58.

    Teller, R. G.; Finke, R. G.; Collman, J. P.; Chin, H. B.; Bau, R. J. Am. Chem. Soc. 1977, 99, 1104.

  59. 59.

    Hocking, R. K.; Hambley, T. W. Organometallics 2007, 26, 2815.

  60. 60.

    Albright, T. A.; Burdett, J. K.; Whangbo, M.-H. Orbital Interactions in Chemistry, 2nd ed.; J. Wiley & Sons: New York, 2013.

  61. 61.

    Ding, S.; Hall, M. B. Struct. Bond. 2016, 169, 199.

  62. 62.

    Gray, H. B.; Beach, N. A. J. Am. Chem. Soc. 1963, 85, 2922.

  63. 63.

    Bunge, C. F.; Barrientos, J. A.; Bunge, A. V. At. Data Nuc. Data Tables 1993, 53, 113.

  64. 64.

    Gristenko, O. V.; Mentel, L. M.; Baerends, E. J. J. Chem. Phys. 2016, 144, #204114, and references therein.

  65. 65.

    Della Sala, F. Theor. Chem. Acc. 2007, 117, 981, and references therein.

  66. 66.

    Fukuda, R.; Hayaki, S.; Nakatsuji, H. J. Chem. Phys. 2009, 131, #174303.

  67. 67.

    Frenking, G.; Fernádez, I.; Holzmann, N.; Pan, S.; Krossing, I.; Zhou, M. J. Am. Chem. Soc. Au 2021, 1, 623.

  68. 68.

    Fukuda, R.; Ehara, M.; Nakatsuji, H.; Kishimoto, N.; Ohno, K. J. Chem. Phys. 2010, 132, #084302.

  69. 69.

    Hummel, P.; Oxgaard, J.; Goodard, W. A., III, Gray, H. B. Inorg. Chem. 2005, 44, 2454.

  70. 70.

    Seiler, P.; Dunitz, J. D. Acta Crystallogr. B 1980, 36, 2946; Borissova, A. O.; Antipin, M. Y.; Perekalin, D. S.; Lyssenko, K. A. CrystEngComm 2008, 10, 827.

  71. 71.

    Drabik, G.; Szklarzwicz, J.; Radon M. Phys. Chem. Chem. Phys. 2021, 23, 151.

  72. 72.

    Xu, Z.-F.; Xie, Y.; Feng, W.-L.; Schaefer, H. F., III J. Phys. Chem. A 2003, 107, 2716, and references therein.

  73. 73.

    Ishimura, K.; Hada, M.; Nakatsuji, H. J. Chem. Phys. 2002, 117, 6533.

  74. 74.

    Cotton, F. A.; Daniels, L. M.; Pascual, I. Acta Crystallogr. C 1998, 54, 1575, and references therein.

  75. 75.

    Bünder, W.; Weiss, E. Z. Naturforsch. B 1978, 33, 1235.

  76. 76.

    Haaland, A. Inorg. Nucl. Chem. Lett. 1979, 15, 267.

  77. 77.

    Green, J. C.; Burney, C. Polyhedron 2004, 23, 2915.

  78. 78.

    Almenningen, A.; Haaland, A.; Samdal, S. J. Organomet. Chem. 1978, 149, 219.

  79. 79.

    Sitzmann, H.; Schär, M.; Dormann, E.; Kelemen, M. Z. Anorg. Allg. Chem. 1997, 623, 1609.

  80. 80.

    Walter, M. D.; Sofield, C. D.; Booth, C. H.; Andersen, R. A. Organometallics 2009, 28, 2005.

  81. 81.

    Poil, R.; Cacelli, I. Eur. J. Inorg. Chem. 2005, 2324.

  82. 82.

    Gard, E.; Haaland, A.; Novak, D. P.; Seip, R. J. Organomet. Chem. 1975, 88, 181.

  83. 83.

    Flower, K. R.; Hitchcock, P. B. J. Organomet. Chem. 1996, 507, 275.

  84. 84.

    Bauer, H.; Weismann, J.; Saurenz, D.; Färber, C.; Schär, M.; Gidt, W.; Schädlich, I.; Wolmershäuser, G.; Sun, Y.; Harder, S.; Sitzmann, H. J. Organomet. Chem. 2016, 809, 63, and references therein.

  85. 85.

    Sitzmann, H.; Schär, M.; Dormann, E.; Kelemen, M. Z. Anorg. Allg. Chem. 1997, 623, 1850.

  86. 86.

    Overby, J. S.; Schoell, N. J.; Hanusa, T. P. J. Organomet. Chem. 1998, 560, 15.

  87. 87.

    Antipin, M. Y.; Boese, R. Acta Crystallogr. B 1996, 52, 314.

  88. 88.

    Jackson, T. A.; Krzystek, J.; Ozarowski, A.; Wijeratne, G. B.; Wicker, B. F.; Mindiola, D. J.; Telser, J. Organometallics, 2012, 31, 8265; Ibid 2014, 33, 1325.

  89. 89.

    Troyanov, S. I.; Antropiusová, H.; Mach, K. J. Organomet. Chem. 1992, 427, 49.

  90. 90.

    Polásek, M.; Kubista, J. J. Organomet. Chem. 2007, 692, 4073.

  91. 91.

    Hitchcock, P. B.; Kerton, F. M.; Lawless, G. A. J. Am. Chem. Soc. 1998, 120, 10264.

  92. 92.

    Horácek, M.; Kupfer, V.; Thewalt, U.; Stepnicka, P.; Polásek, M.; Mach, K. Organometallics 1999, 18, 3572.

  93. 93.

    Meola, G.; Braband, H.; Schmutz, P.; Benz, M.; Spingler, B.; Alberto, R. Inorg. Chem. 2016, 55, 11131.

  94. 94.

    Timms, P. L. J. Chem. Educ. 1972, 49, 782; Middleton, R.; Hull, J. R.; Simpson, S. R.; Tomlinson, C. H.; Timms, P. L. J. Chem. Soc., Dalton Trans. 1973, 120; Skell, P. S.; Williams-Smith, D. J.; McGlinchey, M. J. J. Am. Chem. Soc. 1973, 95, 3337; Silvon, M. P.; Van Dam, E. M.; Skell, P. S. Ibid. 1974, 96, 1945.

  95. 95.

    Astruc, D. Tetrahedron 1983, 39, 4027; Abd-El-Aziz, A. S.; Bernardin, S. Coord. Chem. Rev. 2000, 203, 219; Aranzaes, J. R.; Asruc, D. Inorg. Chim. Acta 2008, 361, 1.

  96. 96.

    Piper, T. S.; Cotton, F. A.; Wilkinson, G. J. Inorg. Nucl. Chem. 1955, 1, 165; Hallam, B. F.; Pauson, P. L. J. Chem. Soc. 1956, 3030; King, R. B.; Stone, F. G. A. Inorg. Synth. 1963, 7, 110.

  97. 97.

    Bryan, R. F.; Greene, P. T.; Newlands, M. J.; Field, D. S. J. Chem. Soc A 1970, 3068.

  98. 98.

    Mitschler, A.; Rees, B.; Lehmann, M. S. J. Am. Chem. Soc. 1978, 100, 3390.

  99. 99.

    Labinger, J. A. Inorg. Chim. Acta 2015, 424, 14.

  100. 100.

    Bullitt, J. G.; Cotton, F. A.; Marks, T. J. Inorg. Chem. 1972, 4, 671; Adams, R. D.; Cotton, F. A. J. Am. Chem. Soc. 1973, 95, 6589.

  101. 101.

    Gansow, O. A.; Burke, A. R.; Vernon, W. D. J. Am. Chem. Soc. 1972, 94, 2550; Ibid. 1976, 98, 5817.

  102. 102.

    Farrugia, L. J.; Musto, L. Organometallics 1992, 11, 2941; Farrugia L. J. J. Chem. Soc, Dalton Trans. 1997, 1783.

  103. 103.

    Fischer, E. O.; Moser, E. Inorg. Synth. 1970, 12, 35.

  104. 104.

    Mattson, B. M.; Graham, W. A. G. Inorg. Chem. 1981, 20, 3186.

  105. 105.

    Reger, D. L.; Coleman, C. J. Organomet. Chem. 1977, 131, 153.

  106. 106.

    M'thiruaine, C. M.; Friedrich, H. B.; Changamu, E. O.; Bala, M. D. Inorg. Chim. Acta 2011, 366, 105.

  107. 107.

    Theys, R. D.; Dudley, M. E.; Hossain, M. M. Coord. Chem. Rev. 2009, 253, 180.

  108. 108.

    Cutler, A. R.; Hanna, P. K.; Vites, J. C. Chem. Rev. 1988, 88, 1363.

  109. 109.

    Grice, K. A. Coord. Chem. Rev. 2017, 336, 78.

  110. 110.

    Davison, A.; Green, M. L. H.; Wilkinson, G. J. Chem. Soc. 1961, 3172; Fischer, E. O.; Fichtel, K. Chem. Ber. 1961, 94, 1200.

  111. 111.

    Singh, M. M.; Angelici, R. J. Inorg. Synth. 1986, 24, 161.

  112. 112.

    Gill, U. S.; Lee, C. C.; Sutherland, R. G. Synth. React. Met.-Org. Chem. 1984, 14, 953.

  113. 113.

    Gress, M. E.; Jacobson, R. A. Inorg. Chem. 1973, 12, 1746.

  114. 114.

    Bitterwolf, T. E. Coord. Chem. Rev. 2000, 206–207, 419, and references therein.

  115. 115.

    Brookes, C. M.; Lomont, J. P.; Nguyen, S. C.; Calladine, J. A.; Sun, X.-Z.; Harris, C. B.; George, M. W. Polyhedron 2014, 72, 130.

  116. 116.

    Blaha, J. P.; Bursten, B. E.; Dewan, J. C.; Frankel, R. B.; Randolph, C. L.; Wilson, B. A.; Wrighton, M. S. J. Am. Chem. Soc. 1985, 107, 4561.

  117. 117.

    Summerville, R. H.; Hoffmann, R. J. Am. Chem. Soc. 1979, 101, 3821.

Author information

Authors and Affiliations

  1. Department of Chemistry, University of Alberta, Edmonton, AB, Canada

    Robert B. Jordan

Authors
  1. Robert B. Jordan
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Robert B. Jordan .

Rights and permissions

Reprints and permissions

Copyright information

© 2024 The Author(s), under exclusive license to Springer Nature Switzerland AG

About this chapter

Check for updates. Verify currency and authenticity via CrossMark

Cite this chapter

Jordan, R.B. (2024). Organometallic Chemistry of Transition Metals. In: Principles of Inorganic Chemistry. Springer, Cham. https://doi.org/10.1007/978-3-031-22926-8_10

Download citation

Publish with us

Policies and ethics

Search

Navigation