Skip to main content
SpringerLink
Log in

Crystal field arguments to explain the trans labilisation within transition metal–borane complexes

  • Published:
Transition Metal Chemistry Aims and scope Submit manuscript

Abstract

There has been great interest in metal–borane complexes following the discovery of metallaboratrane complexes in 1999. These complexes contain unusual Z-type (σ-acceptor) coordination of borane functional groups and have been shown to provide unexpected coordination geometries and properties for a transition metal in a particular oxidation state. Additionally, such ligands exhibit unusually high trans influences only in certain geometries. Herein, a simple qualitative description, based on crystal field theory arguments, is presented for the explanation of the geometries and atypical trans labilisations observed.

Graphical Abstract

Trans labilisation: This discussion highlights the geometries observed within metal–borane complexes and discusses the origin of the labilisation of ligands in the site trans to boron.

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

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Scheme 1
Fig. 7
Fig. 8
Fig. 9
Fig. 10
Fig. 11
Fig. 12

Similar content being viewed by others

References

  1. Hill AF, Owen GR, White AJP, Williams DJ (1999) Angew Chem Int Ed 38:2759

    Article  CAS  Google Scholar 

  2. St. Foreman MRJ, Hill AF, Owen GR, White AJP, Williams DJ (2003) Organometallics 22:4446

    Article  Google Scholar 

  3. St. Foreman MRJ, Hill AF, White AJP, Williams DJ (2004) Organometallics 23:913

    Article  Google Scholar 

  4. Crossley IR, Hill AF (2004) Organometallics 23:5656

    Article  CAS  Google Scholar 

  5. Crossley IR, St. Foreman MRJ, Hill AF, White AJP, Williams DJ (2005) Chem Commun 221

  6. Crossley IR, Hill AF, Willis AC (2005) Organometallics 24:1062

    Article  CAS  Google Scholar 

  7. Crossley IR, Hill AF, Humphrey ER, Willis AC (2005) Organometallics 24:4083

    Article  CAS  Google Scholar 

  8. Crossley IR, Hill AF, Willis AC (2006) Organometallics 25:289

    Article  CAS  Google Scholar 

  9. Crossley IR, Hill AF, Willis AC (2007) Organometallics 26:3891

    Article  CAS  Google Scholar 

  10. Crossley IR, Hill AF, Willis AC (2008) Dalton Trans 201

  11. Crossley IR, Hill AF, Willis AC (2008) Organometallics 27:312

    Article  CAS  Google Scholar 

  12. Crossley R, St. Foreman MRJ, Hill AF, Owen GR, White AJP, Williams DJ, Willis AC (2008) Organometallics 27:381

    Article  CAS  Google Scholar 

  13. Figueroa JS, Melnick JG, Parkin G (2006) Inorg Chem 45:7056

    Article  CAS  Google Scholar 

  14. Pang K, Quan SM, Parkin G (2006) Chem Commun 5015

  15. Mihalcik DJ, White JL, Tanski JM, Zakharov LN, Yap GPA, Incarvito CD, Rheingold AL, Rabinovich D (2004) Dalton Trans 1626

  16. Blagg RJ, Charmant JPH, Connelly NG, Haddow MF, Orpen AG (2006) Chem Commun 2350

  17. Senda S, Ohki Y, Hirayama T, Toda D, Chen J-L, Matsumoto T, Kawaguchi H, Tatsumi K (2006) Inorg Chem 45:9914

    Article  CAS  Google Scholar 

  18. Pang K, Tanski JM, Parkin G (2008) Chem Commun 1008

  19. Landry VK, Melnick JG, Buccella D, Pang K, Ulichny JC, Parkin G (2006) Inorg Chem 45:2588

    Article  CAS  Google Scholar 

  20. Rudolf GC, Hamilton A, Orpen AG, Owen GR (2009) Chem Commun 553

  21. Owen GR, Gould PH, Charmant JPH, Hamilton A, Saithong S (2010) Dalton Trans B911651F

  22. Bontemps S, Gornitzka H, Bouhadir G, Miqueu K, Bourissou D (2006) Angew Chem Int Ed 45:1611

    Article  CAS  Google Scholar 

  23. Bontemps S, Bouhadik G, Miqueu K, Bourissou D (2006) J Am Chem Soc 128:12056

    Article  CAS  Google Scholar 

  24. Sircoglou M, Bontemps S, Mercy M, Saffon N, Takahashi M, Bouhadir G, Maron L, Bourissou D (2007) Angew Chem Int Ed 46:8583

    Article  CAS  Google Scholar 

  25. Bontemps S, Sircoglou M, Bouhadir G, Puschmann H, Howard JAK, Dyer PW, Miqueu K, Bourissou D (2008) Chem Eur J 14:731

    Article  CAS  Google Scholar 

  26. Sircoglou M, Bouhadir G, Saffon N, Miqueu K, Bourissou D (2008) Organometallics 27:1675

    Article  CAS  Google Scholar 

  27. Tsoureas N, Haddow MF, Hamilton A, Owen GR (2009) Chem Commun 2538

  28. Tsoureas N, Bevis T, Butts CP, Hamilton A, Owen GR (2009) Organometallics 28:5222

    Article  CAS  Google Scholar 

  29. Green MLH (1995) J Organomet Chem 500:127

    Article  CAS  Google Scholar 

  30. Hill AF (2006) Organometallics 25:4741

    Article  CAS  Google Scholar 

  31. Parkin G (2006) Organometallics 25:4744

    Article  CAS  Google Scholar 

  32. Shriver DF (1963) J Am Chem Soc 85:3509

    Article  CAS  Google Scholar 

  33. Parshall GW (1964) J Am Chem Soc 86:361

    Article  CAS  Google Scholar 

  34. Johnson MP, Shriver DF (1966) J Am Chem Soc 88:301

    Article  CAS  Google Scholar 

  35. Braunschweig H, Wagner T (1994) Chem Ber 127:1613

    Article  CAS  Google Scholar 

  36. Braunschweig H, Wagner T (1996) Z Naturforsch B 51:1618

    CAS  Google Scholar 

  37. Braunschweig H, Kollann C (1999) Z Naturforsch B 54:839

    CAS  Google Scholar 

  38. Burlitch JM, Leonowicz ME, Peterson RB, Hughes RE (1979) Inorg Chem 18:1097

    Article  CAS  Google Scholar 

  39. Cook KS, Piers WE, McDonald R (1999) Organometallics 18:1575

    Article  CAS  Google Scholar 

  40. Cook KS, Piers WE, McDonald R (2001) Organometallics 20:3927

    Article  CAS  Google Scholar 

  41. Cook KS, Piers WE, McDonald R (2002) J Am Chem Soc 124:5411

    Article  CAS  Google Scholar 

  42. Braunschweig H, Kollann C, Rais D (2006) Angew Chem Int Ed 45:5254

    Article  CAS  Google Scholar 

  43. Westcott SA, Marder TB, Baker RT, Harlow RL, Calabrese JC, Lam KC, Lin Z (2004) Polyhedron 23:2665

    Article  CAS  Google Scholar 

  44. Curtis D, Lesley MJG, Norman NC, Orpen AG, Starbuck J (1999) J Chem Soc Dalton Trans 1687

  45. Braunschweig H, Radacki K, Rais D, Whittell GR (2005) Angew Chem Int Ed 44:1192

    Article  CAS  Google Scholar 

  46. Fehlner TP (2005) Angew Chem Int Ed 44:2056

    Article  CAS  Google Scholar 

  47. Zhu J, Lin Z (2005) Inorg Chem 44:9384

    Article  CAS  Google Scholar 

  48. Braunschweig H (1998) Angew Chem Int Ed 37:1786

    Article  CAS  Google Scholar 

  49. Irvine GI, Lesley MJG, Marder TB, Norman NC, Rice CR, Robins EG, Roper WR, Whittell GR, Wright LJ (1998) Chem Rev 98:2685

    Article  CAS  Google Scholar 

  50. Smith MR III (1999) Prog Inorg Chem 48:505

  51. Braunschweig H, Colling M (2001) Coord Chem Rev 223:1

    Article  CAS  Google Scholar 

  52. Aldrich S, Coombs DL (2004) Coord Chem Rev 248:535

    Article  Google Scholar 

  53. Cambridge Structural Database (November 2009) The longest Rh-PMe3 bond distance with the exception of compounds containing a bridging coordination mode

  54. Kuzu I, Krummenacher I, Armbruster F, Breher F (2008) Dalton Trans 5836

  55. Fontaine F-G, Boudreau J, Thibault M-H (2008) Eur J Inorg Chem 5439

  56. Jörgensen CK (1962) Absorption spectra and chemical bonding in complexes. Pergamon, Oxford

    Google Scholar 

  57. Jörgensen CK (1963) Orbitals in atoms and molecules. Academic Press, London

    Google Scholar 

  58. Pauling L (1939) The nature of the chemical bond. Cornell University Press, Ithaca

    Google Scholar 

  59. Pritchard HO, Skinner HA (1955) Chem Rev 55:745

    Article  CAS  Google Scholar 

  60. Tsoureas N, Owen GR, Hamilton A, Orpen AG (2008) Dalton Trans 6039

Download references

Acknowledgements

The author acknowledges the support from the Ramsay Trust and Royal Society for the provision of British Centenary Ramsay Memorial and Dorothy Hodgkin Research Fellowships.

Author information

Authors and Affiliations

  1. The School of Chemistry, Cantock’s Close, Bristol, UK

    Gareth R. Owen

Authors
  1. Gareth R. Owen
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Gareth R. Owen.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Owen, G.R. Crystal field arguments to explain the trans labilisation within transition metal–borane complexes. Transition Met Chem 35, 221–228 (2010). https://doi.org/10.1007/s11243-009-9317-6

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11243-009-9317-6

Keywords

Search

Navigation