Skip to main content
Log in

CO Substitution in PhCCo3(CO)9 by 4,5-Bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd). Ligand Fluxionality, Kinetics, and X-Ray Structures of PhCCo3(CO)7(bpcd) and \({\text{Co}}_{\text{3}} ({\text{CO)}}_6 [\mu _2 {\text{ - }}\eta ^2 ,\eta ^1 {\text{ - C(Ph)C}} = {\text{C(PPh}}_{\text{2}} ){\text{C(O)CH}}_{\text{2}} {\text{C(O)] - (}}\mu _{\text{2}} {\text{ - PPh}}_{\text{2}})\)

  • Published:
Structural Chemistry Aims and scope Submit manuscript

Abstract

The reaction between the tetrahedrane cluster PhCCo3(CO)9 (1) and the redox-active diphosphine ligand 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd) leads to the replacement of two CO groups and formation of PhCCo3(CO)7(bpcd) (2). Cluster 2 is thermally unstable and readily transforms into the new cluster \({\text{Co}}_{\text{3}} ({\text{CO)}}_6 [\mu _2 {\text{ - }}\eta ^2 :\eta ^1 {\text{ - C(Ph)C}} = {\text{C(PPh}}_{\text{2}} ){\text{C(O)CH}}_{\text{2}} {\text{C(O)] - (}}\mu _{\text{2}} {\text{ - PPh}}_{\text{2}})\) (3). Both clusters 2 and 3 have been isolated and fully characterized in solution by IR and NMR (31P and 13C) spectroscopy. VT 31P NMR data indicate that the bpcd ligand in PhCCo3(CO)7(bpcd) is fluxional in solution, with two chelating and one bridging isomer being observed at 176 K in THF. The kinetics for the conversion of 2 to 3 followed first-order kinetics in 1,2-dichloroethane (DCE). These data, coupled with the reaction rates being retarded in the presence of added CO, and the activation parameters (ΔH = 27.1 ± 0.3 kcal/mol and ΔS = 9 ± 1 eu) support a scheme involving a dissociative CO loss as the rate-limiting step. Clusters 2 and 3 have been structurally characterized by X-ray diffraction analyses. PhCCo3(CO)7(bpcd) crystallizes in the monoclinic space group P21/n: a = 10.731(2) Å, b = 21.743(3) Å, c = 17.143(1) Å, β = 97.522(8)°, V = 3965.4(8) Å3, Z = 4, d calc = 1.552 g · cm−3; R = 0.0598, R w = 0.0671 for 1428 observed reflections with l > 3σ(l). \({\text{Co}}_{\text{3}} ({\text{CO)}}_6 [\mu _2 {\text{ - }}\eta ^2 :\eta ^1 {\text{ - C(Ph)C}} = {\text{C(PPh}}_{\text{2}} ){\text{C(O)CH}}_{\text{2}} {\text{C(O)] - (}}\mu _{\text{2}} {\text{ - PPh}}_{\text{2}})\) crystallizes in the triclinic space group P\(\overline {\text{1}}\) a = 11.572(1) Å, b = 11.702(1) Å, c = 15.227(1) Å, α = 106.716(6)°, β = 90.419(6)°, γ = 103.676(7)°, V = 1912.4(3) Å3, Z = 2, d calc = 1.560 g · cm−3; R = 0.0545, R w = 0.0632 for 3149 observed reflections with l > 3σ(l). The chemistry exhibited by clusters 2 and 3 is compared with related clusters containing the diphosphine ligand 2,3-bis(diphenylphosphino)maleic anhydride (bma).

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

Access this article

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. Watson, W. H.; Nagl, A.; Hwang, S.; Richmond, M. G. J. Organomet. Chem. 1993, 445, 163.

    Google Scholar 

  2. Yang, K.; Bott, S. G.; Richmond, M. G. J. Organomet. Chem. 1993, 454, 273.

    Google Scholar 

  3. Don, M.-J.; Richmond, M. G.; Watson, W. H.; Krawiec, M.; Kashyap, R. P. J. Organomet. Chem. 1991, 418, 231.

    Google Scholar 

  4. Yang, K.; Chien, H.-S.; Richmond, M. G. J. Mol. Catal. 1994, 88, 159.

    Google Scholar 

  5. Schulman, C. L.; Richmond, M. G.; Watson, W. H.; Nagl, J. Organomet. Chem. 1989, 368, 367.

    Google Scholar 

  6. Richmond, M. G.; Kochi, J. K. Inorg. Chem. 1987, 26, 541.

    Google Scholar 

  7. Osella, D.; Milone, L.; Nervi, C.; Ravera, M. J. Organomet. Chem. 1995, 488, 1.

    Google Scholar 

  8. (a) Colbran, S.; Robinson, B. H.; Simpson, J. J. Chem. Soc. Chem. Commun. 1982, 1361; (b) Colbran, S.; Robinson, B. H.; Simpson, J. Organometallics 1983, 2, 952; (c) Colbran, S.; Hanton, L. R.; Robinson, B. H.; Robinson, W. T.; Simpson, J. J. Organomet. Chem. 1987, 330, 415; (d) Worth, G. H.; Robinson, B. H.; Simpson, J. J. Organomet. Chem. 1990, 387, 337; (e) Worth, G. H.; Robinson, B. H.; Simpson, J. Organometallics 1992, 11, 501, 3863.

  9. McAdam, C. J.; Duffy, N. W.; Robinson, B. H.; Simpson, J. Organometallics 1996, 15, 3935 and references therein.

    Google Scholar 

  10. (a) Yang, K.; Smith, J. M.; Bott, S. G.; Richmond, M. G. Inorg. Chim. Acta 1993, 212, 1; (b) Yang, K.; Smith, J. M.; Bott, S. G.; Richmond, M. G. Organometallics 1993, 12, 4779.

    Google Scholar 

  11. (a) Fenske, D.; Becher, H. J. Chem. Ber. 1974, 107, 117; (b) Fenske, D.; Becher, H. J. Chem. Ber. 1975, 108, 2115; (c) Becher, CO Substitution in PhCCo3(CO)9 by bpcd 235 H. J.; Bensmann, W.; Fenske, D. Chem. Ber. 1977, 110, 315; (d) Fenske, D. Angew. Chem. Intern. Ed. Engl. 1976, 15, 381; (e) Bensmann, W.; Fenske, D. Angew. Chem. Intern. Ed. Engl. 1978, 17, 462; (f) Fenske, D. Chem. Ber. 1979, 112, 363; (g) Bensmann, W.; Fenske, D. Angew. Chem. Intern. Ed. Engl. 1979, 18, 677; (h) Fenske, D.; Christidis, A. Angew. Chem., Intern. Ed. Engl. 1981, 20, 129.

    Google Scholar 

  12. (a) Mao, F.; Tyler, D. R.; Keszler, D. J. Amer. Chem. Soc. 1989, 111, 130; (b) Mao, F.; Philbin, C. E.; Weakley, T. J. R.; Tyler, D. R. Organometallics 1990, 9, 1510; (c) Tyler, D. R.; Mao, F. Coord. Chem. Rev. 1990, 97, 119; (d) Tyler, D. R. Account. Chem. Res. 1991, 24, 325; (e) Fei, M.; Sur, S. K.; Tyler, D. R. Organometallics 1991, 10, 419; (f) Mao, F.; Tyler, D. R.; Bruce, M. R. M.; Bruce, A. E.; Rieger, A. L.; Rieger, P. H. J. Amer. Chem. Soc. 1992, 114, 6418; (g) Schut, D. M.; Keana, K. J.; Tyler, D. R.; Rieger, P. H. J. Amer. Chem. Soc. 1995, 117, 8939; (h) Meyer, R.; Schut, D. M.; Keana, K. J.; Tyler, D. R. Inorg. Chim. Acta 1995, 240, 405.

    Google Scholar 

  13. See also Duffy, N. W.; Nelson, R. R.; Richmond, M. G.; Rieger, A. L.; Rieger, P. H.; Robinson, B. H.; Tyler, D. R.; Wang, J. C.; Yang, K. Inorg. Chem. 1998, 37, 4849.

    Google Scholar 

  14. Roedig, A.; Hörnig, L. Chem. Ber. 1955, 88, 2003.

    Google Scholar 

  15. Nestle, M. O.; Hallgren, J. E.; Seyferth, D. Inorg. Synth. 1980, 20, 226.

    Google Scholar 

  16. Seyferth, D.; Hallgren, J. E.; Spohn, R. J.; Williams, G. H.; Nestle, M. O.; Hung, K. J. Organomet. Chem. 1974, 65, 99.

    Google Scholar 

  17. Shriver, D. F. The Manipulation of Air-Sensitive Compounds, McGraw-Hill: New York, 1969.

  18. Mason, M. R.; Smith, J. M.; Bott, S. G.; Barron, A. R. J. Amer. Chem. Soc. 1993, 115, 4971.

    Google Scholar 

  19. Burla, M. C.; Camalli, M.; Cascarano, G.; Giacovazzo, C.; Polidori, G.; Spagna, R.; Viterbo, D. J. Appl. Crystallogr. 1989, 22, 389.

    Google Scholar 

  20. Mo1EN, An Interactive Structure Solution Program, Enraf-Nonius: Delft, The Netherlands, 1990.

  21. Cromer, D.; Waber, J. T. International Tables for X-Ray Crystallography, Kynoch Press: Birmingham, England, 1974; Vol. IV, Table 2.

    Google Scholar 

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

    Google Scholar 

  23. (a) Xia, C.-G.; Bott, S. G.; Richmond, M. G. Inorg. Chim. Acta 1995, 230, 45; (b) Shen, H.; Bott, S. G.; Richmond, M. G. Organometallics 1995, 14, 4625; (c) Shen, H.; Bott, S. G.; Richmond, M. G. J. Chem. Crystallogr. 1998, 28, 385.

    Google Scholar 

  24. (a) Garrou, P. E. Chem. Rev. 1981, 81, 229; (b) Churchill, M. R.; Lashewycz, R. A.; Shapley, J. R.; Richter, S. I. Inorg. Chem. 1980, 19, 1277.

    Google Scholar 

  25. For related 13C NMR studies dealing with CO fluxinality about tetrahedrane clusters, see (a) Wang, S. P.; Chen, A. F. T.; Richmond, M. G.; Schwartz, M. J. Organomet. Chem. 1989, 371, 81; (b) Yuan, P.; Richmond, M. G.; Schwartz, M. Inorg. Chem. 1991, 30, 588, 679; (c) Wang, D.; Shen, H.; Richmond, M. G.; Schwartz, M. Inorg. Chim. Acta 1995, 236, 1.

    Google Scholar 

  26. Dolphin, D.; Wick, A. Tabulation of Infrared Spectral Data, Wiley-Interscience: New York, 1977.

    Google Scholar 

  27. Shen, H.; Bott, S. G.; Richmond, M. G. Inorg. Chim. Acta 1996, 250, 195.

    Google Scholar 

  28. Atwood, J. D. Inorganic and Organometallic Reaction Mechanisms, Brooks/Cole Publishing Co.: Monterey, CA., 1985.

    Google Scholar 

  29. (a) Matheson, T. W.; Robinson, B. H.; Tham, W. S. J. Chem. Soc. (A) 1971, p. 1457; (b) Penfold, B. R.; Robinson, B. H. Account. Chem. Res. 1973, 6, 73.

    Google Scholar 

  30. (a) Matheson, T. W.; Penfold, B. R. Acta Crystallogr. 1977, B33, 1980; (b) Cunninghame, R. G.; Hanton, L. R.; Jensen, S. D.; Robinson, B. H.; Simpson, J. Organometallics 1987, 6, 1470; (c) Aggarwal, R. P.; Connelly, N. G.; Crespo, M. C.; Dunne, B. J.; Hopkins, P. M.; Orpen, A. G. J. Chem. Soc. Dalton Trans. 1992, p. 655.

    Google Scholar 

  31. (a) Shen, H.; Williams, T. J.; Bott, S. G.; Richmond, M. G.; J. Organomet. Chem. 1995, 505, 1; (b) Bott, S. G.; Wang, J. C.; Shen, H.; Richmond, M. G. J. Chem. Crystallogr. 1999, 29, 391.

    Google Scholar 

  32. (a) Colbran, S. B.; Robinson, B. H.; Simpson, J. Acta Crystallogr. 1986, C42, 972; (b) Ahlgr´en, M.; Pakkanen, T. T.; Tahvanainen, I. J. Organomet. Chem. 1987, 323, 91; (c) Xia, C.-G.; Yang, K.; Bott, S. G.; Richmond, M. G. Organometallics 1996, 15, 4480; (d) Castellani, M. P.; Bott, S. G.; Richmond, M. G. J. Chem. Crystallogr. 1998, 28, 693.

    Google Scholar 

  33. (a) Albright, T. A.; Kang, S.-K.; Arif, A. M.; Bard, A. J.; Jones, R. A.; Leland, J. K.; Schwab, S. T. Inorg. Chem. 1988, 27, 1246; (b) Harley, A. D.; Whittle, R. R.; Geoffroy, G. L. Organometallics 1983, 2, 60.

    Google Scholar 

  34. (a) Yang, K.; Bott, S. G.; Richmond, M. G. J. Organomet. Chem. 1996, 516, 65; (b) Yang, K.; Bott, S. G.; Richmond, M. G. Organometallics 1995, 14, 2718.

    Google Scholar 

Download references

Author information

Authors and Affiliations

Authors

Rights and permissions

Reprints and permissions

About this article

Cite this article

Bott, S.G., Shen, H. & Richmond, M.G. CO Substitution in PhCCo3(CO)9 by 4,5-Bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd). Ligand Fluxionality, Kinetics, and X-Ray Structures of PhCCo3(CO)7(bpcd) and \({\text{Co}}_{\text{3}} ({\text{CO)}}_6 [\mu _2 {\text{ - }}\eta ^2 ,\eta ^1 {\text{ - C(Ph)C}} = {\text{C(PPh}}_{\text{2}} ){\text{C(O)CH}}_{\text{2}} {\text{C(O)] - (}}\mu _{\text{2}} {\text{ - PPh}}_{\text{2}})\) . Structural Chemistry 12, 225–235 (2001). https://doi.org/10.1023/A:1016664024371

Download citation

  • Issue Date:

  • DOI: https://doi.org/10.1023/A:1016664024371

Navigation