Skip to main content
SpringerLink
Log in
Book cover

Molecular Electronic Structures of Transition Metal Complexes I pp 17–28Cite as

Electronic Structures of Oxo-Metal Ions

  • Chapter
  • First Online:

Part of the book series: Structure and Bonding ((STRUCTURE,volume 142))

Abstract

The dianionic oxo ligand occupies a very special place in coordination chemistry, owing to its ability to donate π electrons to stabilize high oxidation states of metals. The ligand field theory of multiple bonding in oxo-metal ions, which was formulated in Copenhagen 50 years ago, predicts that there must be an “oxo wall” between Fe–Ru–Os and Co–Rh–Ir in the periodic table. In this tribute to Carl Ballhausen, we review this early work as well as new developments in the field. In particular, we discuss the electronic structures of beyond-the-wall (groups 9 and 10) complexes containing metals multiply bonded to O- and N-donor ligands.

This is a preview of subscription content, 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   169.00
Price excludes VAT (USA)
  • Available as EPUB and PDF
  • Read on any device
  • Instant download
  • Own it forever
Softcover Book
USD   219.99
Price excludes VAT (USA)
  • Compact, lightweight edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info
Hardcover Book
USD   219.99
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

Learn about institutional subscriptions

Notes

  1. 1.

    IUPAC defined a radical as a group of atoms which occurs repeatedly in a number of different compounds.

References

  1. Nugent WA, Mayer JM (1988) Metal-ligand multiple bonds. John Wiley & Sons, New York

    Google Scholar 

  2. Koppel J, Goldmann R (1903) Z Anorg Allg Chem 36:281

    CAS  Google Scholar 

  3. International Union of Pure and Applied Chemistry (1960) J Am Chem Soc 82:5523

    Article  Google Scholar 

  4. International Union of Pure and Applied Chemistry (1970) Nomenclature of inorganic chemistry. Butterworths, London

    Google Scholar 

  5. Ballhausen CJ, Gray HB (1962) Inorg Chem 1:111

    Article  CAS  Google Scholar 

  6. Furman SC, Garner CS (1950) J Am Chem Soc 72:1785

    Article  CAS  Google Scholar 

  7. Furman SC, Garner CS (1951) J Am Chem Soc 73:4528

    Article  CAS  Google Scholar 

  8. Jørgensen CK (1957) Acta Chem Scand 11:73

    Article  Google Scholar 

  9. Hartmann H, Schlafer HL (1954) Angew Chem Int Ed Engl 66:768

    Article  CAS  Google Scholar 

  10. Ballhausen CJ (1962) Introduction to ligand field theory. McGraw-Hill, New York

    Google Scholar 

  11. Bennett RM, Holmes OG (1960) Can J Chem 38:2319

    Article  CAS  Google Scholar 

  12. Hartmann H, Schlafer HL (1951) Z Naturforsch A 6:754

    Google Scholar 

  13. Hartmann H, Schlafer HL (1951) Z Naturforsch A 6:760

    Google Scholar 

  14. Ilse FE, Hartmann H (1951) Z Naturforsch A 6:751

    Google Scholar 

  15. Rossotti FJC, Rossotti HS (1955) Acta Chem Scand 9:1177

    Article  CAS  Google Scholar 

  16. Taube H (1982) In: Rorabacher DB, Endicott JF (eds) Mechanistic Aspects of Inorganic Reactions, vol 198, ACS Symposium Series. American Chemical Society, Washington DC, p 151

    Chapter  Google Scholar 

  17. Selbin J, Ortolano TR, Smith FJ (1963) Inorg Chem 2:1315

    Article  CAS  Google Scholar 

  18. Ballhausen CJ, Djurinski BF, Watson KJ (1968) J Am Chem Soc 90:3305

    Article  CAS  Google Scholar 

  19. Gray HB, Hare CR (1962) Inorg Chem 1:363

    Article  CAS  Google Scholar 

  20. Patterson HH, Nims JL (1972) Inorg Chem 11:520

    Article  CAS  Google Scholar 

  21. Horner SM, Tyree SY (1963) Inorg Chem 2:568

    Article  CAS  Google Scholar 

  22. Weber J, Garner CD (1980) Inorg Chem 19:2206

    Article  CAS  Google Scholar 

  23. Winkler JR, Gray HB (1981) Comments Inorg Chem 1:257

    Article  CAS  Google Scholar 

  24. Hopkins MD, Miskowski VM, Gray HB (1986) J Am Chem Soc 108:6908

    Article  CAS  Google Scholar 

  25. Mohammed AK, Fronczek FR, Maverick AW (1994) Inorg Chim Acta 226:25

    Article  CAS  Google Scholar 

  26. Mohammed AK, Maverick AW (1992) Inorg Chem 31:4441

    Article  CAS  Google Scholar 

  27. Winkler JR (1984) Spectroscopy and Photochemistry of Metal-Oxo Complexes, Ph.D. California Institute of Technology, California

    Google Scholar 

  28. Strickler SJ, Berg RA (1962) J Chem Phys 37:814

    Article  CAS  Google Scholar 

  29. Tanabe Y, Sugano S (1954) J Phys Soc Jpn 9:753

    Article  CAS  Google Scholar 

  30. Tanabe Y, Sugano S (1954) J Phys Soc Jpn 9:766

    Article  CAS  Google Scholar 

  31. Winkler JR, Rice SF, Gray HB (1981) Comments Inorg Chem 1:47

    Article  CAS  Google Scholar 

  32. Sinnecker S, Svensen N, Barr EW, Ye S, Bollinger JM Jr, Neese F, Krebs C (2007) J Am Chem Soc 129:6168

    Article  CAS  Google Scholar 

  33. Riggs-Gelasco PJ, Price JC, Guyer RB, Brehm JH, Barr EW, Bollinger JM, Krebs C (2004) J Am Chem Soc 126:8108

    Article  CAS  Google Scholar 

  34. Price JC, Barr EW, Tirupati B, Bollinger JM, Krebs C (2003) Biochemistry 42:7497

    Article  CAS  Google Scholar 

  35. Hay-Motherwell RS, Wilkinson G, Hussain-Bates B, Hursthouse MB (1993) Polyhedron 12:2009

    Article  CAS  Google Scholar 

  36. Poverenov E, Efremenko I, Frenkel AI, Ben-David Y, Shimon LJW, Leitus G, Konstantinovski L, Martin JML, Milstein D (2008) Nature 455:1093

    Article  CAS  Google Scholar 

  37. Laskowski CA, Miller AJM, Hillhouse GL, Cundari TR (2011) J Am Chem Soc 133:771

    CAS  Google Scholar 

Download references

Acknowledgments

We dedicate this paper to the memory of Carl Ballhausen, a great scientist and a dear friend (Fig. 5). We note in closing that the B&G model is providing a firm foundation for structure/reactivity correlations in our current work on oxo-metal complexes [oxidative enzymes P450 and nitric oxide synthase (NIH DK019038, GM068461); water oxidation catalysts (NSF CCI Solar Program, CHE-0947829); and trans-dioxo osmium(VI) electrochemistry and photochemistry (BP)]. We thank the Gordon and Betty Moore Foundation and the Arnold and Mabel Beckman Foundation for support of our research programs.

Author information

Authors and Affiliations

  1. Beckman Institute, California Institute of Technology, Pasadena, CA, 91125, USA

    Jay R. Winkler & Harry B. Gray

Authors
  1. Jay R. Winkler
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Harry B. Gray
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Harry B. Gray .

Editor information

Editors and Affiliations

  1. St. Edmund Hall, Oxford, OX1 4AR, United Kingdom

    David Michael P. Mingos

  2. The Royal Institution of Great Britain, Albermarle Street 21, London, W1X 4BS, United Kingdom

    Peter Day

  3. Technical University of Denmark, Copenhagen, Denmark

    Jens Peder Dahl

Rights and permissions

Reprints and permissions

Copyright information

© 2011 Springer-Verlag Berlin Heidelberg

About this chapter

Cite this chapter

Winkler, J.R., Gray, H.B. (2011). Electronic Structures of Oxo-Metal Ions. In: Mingos, D., Day, P., Dahl, J. (eds) Molecular Electronic Structures of Transition Metal Complexes I. Structure and Bonding, vol 142. Springer, Berlin, Heidelberg. https://doi.org/10.1007/430_2011_55

Download citation

Publish with us

Policies and ethics

Search

Navigation