Skip to main content
SpringerLink
Log in

Hitting Two Birds with One Stone: Crystal Containing Both Disproportionation Products of the Mixed-Valence Ruthenium(II, III) Carboxylate

  • Published:
Journal of Cluster Science Aims and scope Submit manuscript

Abstract

The disproportionation of the mixed-valence diruthenium(II, III) trifluoroacetate, [Ru2(O2CCF3)5] (1), is reported. The overall conversion leads to the triruthenium(II, III, III) and diruthenium(II, II) species according to the scheme: 4 Ru2 5+→ 2 Ru3 8+ + Ru2 4+. Both disproportionation products have been isolated and structurally characterized as they cocrystallize in a 2:1 ratio in the form of the acetone adducts to give the complex [Ru3O(O2CCF3)6·(OCMe2)3]2 [Ru2(O2CCF3)4·(OCMe2)2] (2). Compound 2 conforms to the triclinic space group, P 1 (No. 2), with the parameters a = 9. 9238(5) Å, b = 12. 8388(7) Å, c = 20. 1188(10) Å, α = 103. 1390(10)°, β = 103. 1210(10)°, γ = 98. 1650(10)°, V = 2379. 8(2) Å3, and Z = 1. The refinement of 747 parameters and 90 restraints resulted in the final R 1 value of 0. 0454 and wR 2 = 0. 0971 for 8003 reflections with I ≥ 2σ(I), and R 1 value of 0. 0697 and wR 2 = 0. 1071 for all 10, 755 data. The oxidized form is represented by a mixed-valence trinuclear ruthenium complex, [Ru3O(O2CCF3)6·(OCMe2 )3] (2a). This neutral complex possesses a μ3-oxo-centered Ru3O unit with peripheral ligands provided by bridging carboxylates and terminal acetone groups. The core dimensions of 2a indicate a valence-detrapped state in the range of temperatures 295–90 K. The central unit consists of a nearly equilateral triangular array with the Ru–O(oxo) bond distances of 1. 909(3), 1. 905(3), and 1. 910(3) Å. The reduced form, [Ru2(O2CCF3)4·(OCMe2)2] (2b), is a typical tetrabridged diruthenium(II, II) carboxylate having coordinated acetone molecules at both axial sites. The Ru–Ru double bond in the paddlewheel unit is measured at 2. 2858(8) Å. The mechanistic aspects of the disproportionation and the core conversion in 1 as well as in similar metal trifluoroacetates are discussed.

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. (a)H. Miyasaka, R. Clerac, C. S. Campos-Fernandez, and K. R. Dunbar (2001). J. Chem. Soc., Dalton Trans.858. (b)H. Miyasaka, R. Clerac, C. S. Campos-Fernan-dez, and K. R. Dunbar (2001). Inorg. Chem. 40, 1663. (c)D. Yoshioka, M. Mikuriya, and M. Handa (2002). Chem. Lett. 1044. (d)M. C. Barral, R. Gonzalez-Prieto, R. Jimenez-Aparicio, J. L. Priego, M. R. Torres, and F. A. Urbanos (2003). Eur. J. Inorg. Chem. 2339. (e)Y. Sayama, M. Handa, M. Mikuriya, I. Hiromitsu, and K. Kasuga 448 Dikarev and Li. (2003). Bull. Chem. Soc. Jpn. 76, 769. (f)M. W. Cooke, T. S. Cameron, K. N. Robertson, J. C. Swarts, and M. A. S. Aquino (2002). Organometallics 21, 5962.

    Google Scholar 

  2. M. A. S. Aquino (1998). Coord. Chem. Rev. 170, 141.

    Google Scholar 

  3. (a)M. C. Barral, R. Jimenez-Aparicio, D. Perez-Quintanilla, J. L. Priego, E. C. Royer, M. R. Torres, and F. A. Urbanos (2000). Inorg. Chem. 39, 65. (b)M. Handa, Y. Sayama, M. Mikuriya, R. Nukada, I. Hiromitsu, and K. Kasuga (1998). Bull. Chem. Soc. Jpn. 71, 119. (c)F. A. Cotton, J. Lu, and A. Yokochi (1998). Inorg. Chim. Acta 275, 447. (d)M. W. Cooke, C. A. Murphy, T. S. Cameron, E. J. Beck, G. Vamvounis, and M. A. S. Aquino (2002). Polyhedron 21, 1235.

  4. M. C. Barral, R. Jimenez-Aparicio, E. C. Royer, M. J. Saucedo, F. A. Urbanos, E. Gutierrez-Puebla, and C. Ruiz-Valero (1991). J. Chem. Soc., Dalton Trans.1609.

  5. (a)M. C. Barral, R. Jimenez-Aparicio, E. C. Royer, F. A. Urbanos, A. Monge, and C. Ruiz-Valero (1991). Polyhedron 10, 113. (b)B. K. Das and A. R. Chakravarty (1991). Inorg. Chem. 30, 4978.

  6. (a)F. A. Cotton, V. M. Miskowski, and B. Zhong (1989). J. Am. Chem. Soc. 111, 6177. (b)M. C. Barral, R. Jimenez-Aparicio, J. L. Priego, E. C. Royer, F. A. Urbanos, and U. Amador (1998). Inorg. Chim. Acta 279, 30. (c)M. C. Barral, R. Jimenez-Aparicio, J. L. Priego, E. C. Royer, M. J. Saucedo, F. A. Urbanos, and U. Amador (1995). Polyhedron 14, 2419.

  7. F. A. Cotton, L. Labella, and M. Shang (1992). Inorg. Chim. Acta 197, 149.

    Google Scholar 

  8. F. A. Cotton, M. Matusz, and B. Zhong (1988). Inorg. Chem. 27, 4368.

    Google Scholar 

  9. R. W. Mitchell, A. Spencer, and G. Wilkinson (1973). J. Chem. Soc., Dalton Trans.846.

  10. A. Bino, F. A. Cotton, and T. R. Felthouse (1979). Inorg. Chem. 18, 2599.

    Google Scholar 

  11. (a)F. A. Cotton and J. G. Norman Jr. (1972). Inorg. Chim. Acta 6, 411. (b)S. B. Marr, R. O. Carvel, D. T. Richens, H. Lee, M. Lane, and P. Stavropoulos (2000). Inorg. Chem. 39, 4630.

  12. (a)K. Ota, H. Sasaki, T. Matsui, T. Hamaguchi, T. Yamaguchi, T. Ito, H. Kido, and C. P. Kubiak (1999). Inorg. Chem. 38, 4070(b)M. Abe, Y. Sasaki, Y. Yamada, K. Tsukahara, S. Yano, T. Yamaguchi, M. Tominaga, I. Taniguchi, and T. Ito (1996). Inorg. Chem. 35, 6724. (c)T. Yamaguchi, N. Imai, T. Ito, and C. P. Kubiak (2000). Bull. Chem. Soc. Jpn. 73, 1205.

  13. (a)F. A. Cotton, G. E. Lewis, and G. N. Mott (1982). Inorg. Chem. 21, 3316(b) V. I. Ponomarev, O. S. Filipenko, L. O. Atovmyan, S. A. Bobkova, and K. I. Turte (1982). Dokl. Akad. Nauk SSSR 262, 346. (c)V. I. Ponomarev, K. I. Turte, G. V. Shilov, S. A. Bobkova, L. O. Atovmyan, and R. A. Stukan (1986). Koord. Khim. 12, 398. (d)F. A. Cotton, M. W. Extine, L. R. Falvello, D. B. Lewis, G. E. Lewis, C. A. Murillo, W. Schwotzer, M. Tomas, and J. M. Troup (1986). Inorg. Chem. 25, 3505. (e)A. E. Tapper, J. R. Long, R. J. Staples, and P. Stavropoulos (2000). An-gew. Chem. Int. Ed. 39, 2343. (f)K. S. Gavrilenko, A. Vertes, G. Vanko, L. F. Kiss, A. W. Addison, T. Weyhermuller, and V. V. Pavlishchuk (2002). Eur. J. Inorg. Chem. 3347. (g)H. Zhao, C. P. Berlinguette, J. Bacsa, S. E. Tichy, and K. R. Dun-bar (2003). J. Cluster Sci. 14, 235.

  14. (a)A. J. Lindsay, G. Wilkinson, M. Motevalli, and M. B. Hursthouse (1987). J. Chem. Soc., Dalton Trans.2723. (b)A. Cogne, E. Belorizky, J. Laugier, and P. Rey (1994). Inorg. Chem. 33, 3364. (c)H. Miyasaka, C. S. Campos-Fernandez, R. Clerac, and K. R. Dunbar (2000). Angew. Chem. Int. Ed. 39, 3831.

  15. E. V. Dikarev and B. Li (2004). Inorg. Chem. 43, 3461.

    PubMed  Google Scholar 

  16. (a)V. V. Grushin, W. J. Marshall, and D. L. Thorn (2001). Adv. Synth. Catal. 343, 161. (b)V. V. Grushin, W. J. Marshall, and D. L. Thorn (2001). Adv. Synth. Catal. 343, 433.

  17. F. A. Cotton and E. V. Dikarev (1995). J. Cluster Sci. 6, 411.

    Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Department of Chemistry, University at Albany, Albany, NY, 12222, U. S. A

    Evgeny V. Dikarev & Bo Li

Authors
  1. Evgeny V. Dikarev
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Bo Li
    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

Dikarev, E.V., Li, B. Hitting Two Birds with One Stone: Crystal Containing Both Disproportionation Products of the Mixed-Valence Ruthenium(II, III) Carboxylate. Journal of Cluster Science 15, 437–449 (2004). https://doi.org/10.1007/s10876-004-5767-3

Download citation

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10876-004-5767-3

Search

Navigation