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DOI: 10.1039/A805338C (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1998, 3437-3442

Synthesis and characterization of volatile cerium(IV) hexafluoroisopropoxide complexes. Structure of [Hpmdien]2[Ce{OCH(CF3)2}6]

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Liliane G. Hubert-Pfalzgraf, Valérie Abada and Jacqueline Vaissermann

Abstract

The reaction between the cerium isopropoxide [Ce2(OPri)8(PriOH)2] and hexafluoroisopropyl alcohol (Hhfip) in THF at room temperature resulted in the formation of [Ce(hfip)4(THF[hair space])2(PriOH)x]. More stable compounds namely [Ce(hfip)4(diglyme)], [Ce(hfip)4(bipy)2] and [Ce(hfip)4(tmen)] were obtained if the alcoholysis was achieved in the presence of a Lewis base (diglyme = 2,5,8-trioxanonane, bipy = 2,2′-bipyridine, tmen = N,N,N[hair space]′,N[hair space]′-tetramethylethane-1,2-diamine). The use of N,N,N[hair space]′,N[hair space]″,N[hair space]″-pentamethyldiethylenetriamine (pmdien) afforded [Hpmdien]2[Ce(hfip)6] and [Ce(hfip)3(OPri)(pmdien)]. All compounds were volatile and characterized by elemental analyses, FT-IR, 1H and 19F NMR. The pmdien salt was also characterized by X-ray diffraction. The cerium atom is six-co-ordinated [Ce–O 2.183(5)–2.208(5) Å] with the CF3 groups forming nearly a crown (Ce[hair space][hair space]· · ·[hair space][hair space]F 4.06–4.32 Å). The metallic anion [Ce(hfip)6]2– and the [Hpmdien]+ cations are associated by a short F[hair space][hair space]· · ·[hair space][hair space]C contact (3.15 Å). The interactions are retained in solution as evidenced by 1H and 19F NMR.

References

  1. F. Cerwinski and J. A. Szpunar, J. Sol-gel Sci. Technol., 1997, 9, 103 Search PubMed.
  2. S. Guo, H. Arwin, S. N. Jacobson, K. Järrendahl and V. Helmersson, J. Appl. Phys., 1995, 77, 1829; C. D. Hogarth and Z. T. Al-Dhhan, Phys. Status Solidi, 1986, 137, K 157 Search PubMed; K. Fujiuru, Y. Nishida, K. Kobayashi and S. Takahashi, Optical Wave Guide Materials Mater. Res. Soc. Symp. Proc., 1992, 244 Search PubMed; M. Dejneka, R. E. Riman and E. Snitzer, J. Am. Ceram. Soc., 1994, 76, 3147.
  3. M. A. A. M. van Wijck, M. A. J. Verhoeven, E. M. C. M. Reuvekamp, G. J. Gerritsma, D. H. A. Blank and H. Rogalla, Appl. Phys. Lett., 1996, 68, 553 CrossRef CAS; M. Becht, J. G. Wen, T. Morishita and K. Tanabe, Chemical Vapor Deposition, Proceedings of the XIV International Conference and EuroCVD-11, eds. M. D. Allendorf and C. Bernard, the Electrochemical Society, Pennington, 1997, 97–25, 756 Search PubMed.
  4. G. Blasse, Chem. Mater., 1994, 6, 1465 CrossRef CAS.
  5. (a) L. G. Hubert-Pfalzgraf, New. J. Chem., 1995, 19, 727 Search PubMed; (b) L. G. Hubert-Pfalzgraf and H. Guillon, Appl. Organomet. Chem., 1998, 12, 321 CrossRef; (c) H. Guillon, Ph.D. Thesis, Université de Nice, February 1998.
  6. H. A. Stecher, A. Sen and A. L. Rheingold, Inorg. Chem., 1988, 27, 1130 CrossRef CAS; 1989, 28, 3280.
  7. E. Uhlemann and F. Diandze, Z. Anorg. Allg. Chem., 1971, 386, 329 CrossRef CAS; M. Becht, T. Gerfin and K. H. Dahmen, Chem. Mater., 1993, 5, 137 CrossRef CAS.
  8. J. McAleese, J. C. Plakatouras and B. C. H. Steele, Thin Solids Films, 1996, 280, 152 Search PubMed.
  9. J. McAleese, J. A. Darr and B. C. H. Steele, Chem. Vap. Deposition, 1996, 2, 244 CAS.
  10. I. Baxter, J. A. Darr, M. B. Hursthouse, K. M. A. Malik, J. Mc Aleese and D. M. P. Mingos, Polyhedron, 1998, 17, 1329 CrossRef CAS.
  11. F. Labrize, L. G. Hubert-Pfalzgraf and J. C. Daran, J. Chem. Soc., Chem. Commun, 1993, 1556 RSC; F. Labrize, L. G. Hubert-Pfalzgraf, J. C. Daran and P. Tobaly, Polyhedron, 1995, 14, 881 CrossRef CAS; H. Vincent, F. Labrize and L. G. Hubert-Pfalzgraf, Polyhedron, 1994, 13, 3223 CrossRef CAS.
  12. D. C. Bradley, H. Chudzynska, M. E. Hammond, M. B. Hursthouse, M. Motevalli and W. Ruowen, Polyhedron, 1992, 11, 375 CrossRef CAS; D. C. Bradley, H. Chudzynska, M. B. Hursthouse, M. Motevalli and R. Wu, Polyhedron, 1993, 12, 2955 CrossRef CAS; D. C. Bradley, H. Chudzynska, M. B. Hursthouse and M. Motevalli, Polyhedron, 1994, 13, 7 CrossRef CAS; D. C. Bradley, H. Chudzynska, M. B. Hursthouse, M. Motevalli and R. Wu, Polyhedron, 1994, 13, 1 CrossRef CAS.
  13. J. A. Samuels, E. B. Lobkowsky, W. E. Streib, K. Folting, J. C. Huffman, J. W. Zwanziger and K. G. Caulton, J. Am. Chem. Soc., 1993, 115, 5093 CrossRef CAS.
  14. B. A. Vaartstra, J. C. Huffman, P. S. Gradeff, L. G. Hubert-Pfalzgraf, J. C. Daran, S. Parraud, K. Yunlu and K. G. Caulton, Inorg. Chem., 1990, 29, 3126 CrossRef.
  15. D. J. Watkin, C. K. Prout, J. R. Carruthers and P. W. Betteridge, Crystals Issue 10, Chemical Crystallography Laboratory, University of Oxford, 1996 Search PubMed.
  16. D. T. Cromer, International Tables for X-Ray Crystallography, Kynoch Press, Birmingham, 1974, vol. 4 Search PubMed.
  17. J. Fischer, W. G. van der Sluys, J. C. Huffman and J. Sears, Synth. React. Inorg. Metal. Org. Chem., 1993, 23, 479 Search PubMed; C. Campbell, S. G. Bott, R. Larsen and W. G. Van der Sluys, Inorg. Chem., 1994, 33, 4950 CrossRef CAS.
  18. I. Baxter, S. R. Drake, M. B. Hursthouse, K. M. A. Malik, J. MacAleese, D. J. Otway and J. C. Plakatouras, Inorg. Chem., 1995, 34, 1384 CrossRef CAS; A. Drozdov and S. Troyanov, Polyhedron, 1993, 12, 2973 CrossRef CAS; S. R. Drake, S. A. S. Miller and D. J. Williams, Inorg. Chem., 1993, 32, 3227 CrossRef.
  19. C. Sirio, L. G. Hubert-Pfalzgraf and C. Bois, Polyhedron, 1997, 16, 1129 CrossRef CAS.
  20. J. L. Kiplinger, T. G. Richmond and C. E. Osterberg, Chem. Rev., 1994, 94, 373 CrossRef CAS.
  21. J. A. Darr, S. R. Drake, M. B. Hursthouse, K. M. A. Malik, S. A. S. Miller and M. P. Mingos, J. Chem. Soc., Dalton Trans., 1997, 945 RSC.
  22. H. Strauss, Chem. Rev., 1993, 93, 927 CrossRef CAS; K. Seppelt, Angew. Chem., Int. Ed. Engl., 1993, 32, 1025 CrossRef; C. Reed, Acc. Chem. Res., 1998, 31, 133 CrossRef CAS.
  23. J. J. Roekwell, G. M. Kloster, W. J. Duboy, P. A. Grieco, D. F. Shriver and S. H. Strauss, Inorg. Chim. Acta, 1997, 263, 195 CrossRef.
  24. J. H. Burns and M. D. Danford, Inorg. Chem., 1969, 8, 1780 CrossRef CAS.
  25. M. Becht, K. H. Dahmen, V. Gramlich and A. Marteletti, Inorg. Chim. Acta, 1996, 248, 27 CrossRef CAS.
  26. R. E. Sievers, K. J. Eisentraut and C. S. Springer, Adv. Chem. Ser., 1967, 71, 141 Search PubMed.
  27. K. D. Pollard, J. J. Vittal, G. P. A. Yap and R. J. Puddephatt, J. Chem. Soc., Dalton Trans., 1998, 1265 RSC.
  28. R. E. Sievers, S. B. Turnipseed, L. Huang and A. F. Lagalante, Coord. Chem. Rev., 1993, 128, 285 CrossRef CAS.
  29. S. Suh and D. M. Hoffman, Inorg. Chem., 1996, 35, 6164 CrossRef CAS.
  30. M. H. Chisholm, J. C. Huffman and J. L. Wesemann, Polyhedron, 1991, 10, 1367 CrossRef CAS.