Skip to main content
SpringerLink
Log in

Chelation of a diphosphine ligand at FeCo2(CO)9(μ3-S): Spectroscopic and X-ray diffraction data for FeCo2(CO)7(bpcd)(μ3-S)

  • Published:
Journal of Chemical Crystallography Aims and scope Submit manuscript

Abstract

The tetrahedrane cluster, FeCo2(CO)9(μ3-S), reacts with the redox-active ligand, 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd), to give the disubstituted cluster, FeCo2(CO)7(bpcd)(μ3-S), as the sole product. This diphosphine-substituted cluster contains a cobalt-bound, chelating bpcd ligand. Both IR and 31P NMR spectroscopies have been employed in the solution characterization of FeCo2(CO)7(bpcd)(μ3-S), and the solid-state structure has been unequivocally established by X-ray diffraction analysis. FeCo2(CO)7(bpcd)(μ3-S) crystallizes in the monoclinic space group C2/c, a = 34.494(3) Å, b = 11.4194(9) Å, c = 18.634(2) Å, β = 98.103(7)°, V = 7266.7(9) Å3, Z = 8, and dcalc = 1.584 g/cm3. Cyclic voltammetric studies on FeCo2(CO)7(bpcd)(μ3-S) reveal the presence of two quasireversible redox responses assigned to the 0/1− and 1−/2− redox couples. The orbital composition of these redox couples has been examined by carrying out extended Hückel MO calculations on the model complex FeCo2(CO)7(H4-bpcd)(μ3-S), with the results being compared to related cluster compounds.

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

Similar content being viewed by others

References

  1. Braunstein, P.; Rosé, J. In Catalysis by Di-and Polynuclear Metal Cluster Complexes, Adams, R.D.; Cotton, F.A., Eds.; Wiley-VCH: New York, 1998; Chap. 13.

    Google Scholar 

  2. Gladfelter, W.L.; Geoffroy, G.L. Adv. Organomet. Chem. 1980, 18, 207.

    Google Scholar 

  3. Don, M.J.; Richmond, M.G.; Watson, W.H.; Krawiec, M.; Kashyap, R.P. J. Organomet. Chem. 1991, 418, 231. (b) Watson, W.H.; Nagl, A.; Hwang, S.; Richmond, M.G. J. Organomet. Chem. 1993, 445, 163. (c) Yang, K.; Bott, S.G.; Richmond, M.G. J. Organomet. Chem. 1993, 454, 273.

    Google Scholar 

  4. Yang, K.; Smith, J.M.; Bott, S.G.; Richmond, M.G. Organometallics 1993, 12, 4779. (b) Shen, H.; Bott, S.G.; Richmond, M.G. Inorg. Chim. Acta 1996, 250, 195.

    Google Scholar 

  5. Vahrenkamp, H. Inorg. Synth. 1989, 26, 352.

    Google Scholar 

  6. Fenske, D.; Becher, H.J.; Chem. Ber. 1975, 108, 2115.

    Google Scholar 

  7. Bard, A.J.; Faulkner, L.R. Electrochemical Methods, Wiley: New York, 1980.

    Google Scholar 

  8. Hoffmann, R.; Lipscomb, W.N. J. Chem. Phys. 1962, 36, 2179. (b) Hoffmann, R. J. Chem. Phys. 1963, 39, 1397.

    Google Scholar 

  9. Mealli, C.; Proserpio, D.M. J. Chem. Ed. 1990, 67, 399.

    Google Scholar 

  10. Weast, R.C. (Ed.) Handbook of Chemistry and Physics, CRC Press: Cleveland, OH, 56th ed., 1975.

    Google Scholar 

  11. Koelle, U. J. Organomet. Chem. 1977, 133, 53. (b) Albers, M.O.; Coville, N.J. Coord. Chem. Rev. 1984, 53, 227.

    Google Scholar 

  12. Shen, H.; Bott, S.G.; Richmond, M.G. Organometallics 1995, 14, 4625.

    Google Scholar 

  13. We have only shown the two most likely possibilities of FeCo2 (CO)7(bpcd)(µ 3-S) that would display equivalent 31P centers.

  14. Richmond, M.G.; Kochi, J.K. Inorg. Chem. 1986, 25, 1334.

    Google Scholar 

  15. Aime, S.; Milone, L.; Rossetti, R.; Stanghellini, P.L. Inorg. Chim. Acta 1977, 25, 103.

    Google Scholar 

  16. Colbran, S.B.; Robinson, B.; Simpson, J. Acta Crystallogr. 1986, C42, 972. (b) Ahlgre´ n, M.; Pakkanen, T.T.; Tahvanainen, I. J. Organomet. Chem. 1987, 323, 91. (c) Richter, F.; Vahrenkamp, H. Angew. Chem. Int. Ed. Eng. 1978, 17, 444. (d) Steveson, D.L.; Wei, C.H.; Dahl, L.F. J. Am. Chem. Soc. 1971, 93, 6027.

    Google Scholar 

  17. Richter, F.; Vahrenkamp, H. Chem. Ber. 1982, 115, 3243. (b) Richter, F.; Roland, E.; Vahrenkamp, H. Chem. Ber. 1984, 117, 2429. (c) Richter, F.; Vahrenkamp, H.; Organometallics 1982, 1, 756.

    Google Scholar 

  18. Don, M.-J.; Richmond, M.G.; Watson, W.H.; Kashyap, R.P. Acta Crystallgr. 1991, C47, 20. (b) Downard, A.J.; Robinson, B.H.; Simpson, J. Organometallics 1986, 5, 1122.

    Google Scholar 

  19. Honrath, U.; Vahrenkamp, H. Z. Naturforsch. 1984, 39B, 545.

    Google Scholar 

  20. Peake, B.M.; Rieger, P.H.; Robinson, B.H.; Simpson, J. Inorg. Chem. 1981, 20, 2540. (b) Bond, A.H.; Peake, B.M.; Robinson, B.H.; Simpson, J. Inorg. Chem. 1977, 16, 410. (c) Peake, B.M.;Robinson, B.H.; Simpson, J.; Watson, D.J. Inorg. Chem. 1977, 16, 405. (d) Peake, B.M.; Rieger, P.H.; Robinson, B.H.; Simpson, J. Inorg. Chem. 1979, 18, 1000.

    Google Scholar 

  21. Schilling, B.E.R.; Hoffmann, R. J. Am. Chem. Soc. 1979, 101, 3456. (b) Chesky, P.T.; Hall, M.B. Inorg. Chem. 1981, 20, 4419.

    Google Scholar 

  22. Schut, D.M.; Keana, K.J.; Tyler, D.R.; Rieger, P.H. J. Am. Chem. Soc., 1995, 117, 8939. (b) Meyer, R.; Schut, D.M.; Keana, K.J.; Tyler, D.R. Inorg. Chim. Acta 1995, 240, 405.

    Google Scholar 

  23. Albright, T.A.; Burdett, J.K.; Whangbo, M.H. Orbital Interactions in Chemistry, Wiley: New York, 1985.

    Google Scholar 

  24. Unpublished results.

Download references

Author information

Authors and Affiliations

  1. Department of Chemistry, University of Houston, Houston, Texas, 77204

    Simon G. Bott

  2. Department of Chemistry, University of North Texas, Denton, Texas, 76203

    Jian Cheng Wang, Huafeng Shen & Michael G. Richmond

Authors
  1. Simon G. Bott
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Jian Cheng Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Huafeng Shen
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Michael G. Richmond
    View author publications

    You can also search for this author in PubMed Google Scholar

Rights and permissions

Reprints and permissions

About this article

Cite this article

Bott, S.G., Wang, J.C., Shen, H. et al. Chelation of a diphosphine ligand at FeCo2(CO)9(μ3-S): Spectroscopic and X-ray diffraction data for FeCo2(CO)7(bpcd)(μ3-S). Journal of Chemical Crystallography 29, 391–397 (1999). https://doi.org/10.1023/A:1009502708303

Download citation

  • Issue Date:

  • DOI: https://doi.org/10.1023/A:1009502708303

Search

Navigation