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Octahedral Niobium Thiocyanato Complexes Containing [Nb6Cl9O3] Cluster Core: Syntheses, Crystal Structures and Evidences of NCS Ligand Exchange

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Abstract

Two isomers (cis and trans) of [Nb6Cl9O3(NCS)6]5– niobium cluster complexes characterized by an ordered arrangement of oxygen and chlorine ligands over the 12 inner positions in the cluster core were prepared by reaction of Cs2LaNb6Cl15O3 and ScNb6Cl13O3 solid state compounds with aqueous solution of potassium thiocyanate. The cis and trans isomers (idealized C 2 v and D 3 symmetry, respectively) crystallize with counter cations and water molecules to form the following salts: Cs4.75K0.25[Nb6Cl9O3(NCS)6] · 5.5H2O (1) and Cs2.5K2.5[Nb6Cl9O3(NCS)6] · 2H2O (2), respectively. The trans isomer is ordered in structure 1 (s.g.: C2/c), while in the structure of 2 (s.g.: Pnma), the cis isomer is randomly disordered over two positions that correspond one to each other by a mirror plane. Interestingly, the treatment of thiocyanato complexes cis and trans with hydrochloric acid led to substitution of (NCS)– ligands by Cl– and to formation of soluble complexes [Nb6Cl9O3Cl6]5–. The cesium salt of trans-[Nb6Cl9O3Cl6]5– was crystallized as Cs5[Nb6Cl15O3] · CsCl · 7H2O (3) and structurally characterized. Indeed, the formation of soluble [Nb6Cl9O3(NCS)6]5– intermediates is a necessary step towards the formation of soluble \(\left[ {{\text{Nb}}_{6}{\text{Cl}^{\rm{i}}}_{ 9}{\text{O}}^{\rm{i}}{\,}_{3}{\text{Cl}}^{\rm{a}}{\,}_{6}}\right]^{5-} \) anions.

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References

  1. N. Prokopuk and D. F. Shriver (1999). Adv. Inorg. Chem. 46, 1.

    Article  Google Scholar 

  2. C. Perrin (1997). J. Alloys Compd. 262, 10.

    Article  Google Scholar 

  3. A. Simon and F. Ueno (1985). Acta Crystallogr. C41, 308.

    Google Scholar 

  4. J. D. Corbett (1995). J. Alloys Compd. 229, 10.

    Article  CAS  Google Scholar 

  5. A. Simon, H. G. von Schnering, and H. Schaefer (1967). Z. Anorg. Allg. Chem. 355, 295.

    Article  CAS  Google Scholar 

  6. H. Imoto and J. D. Corbett (1980). Inorg. Chem. 19, 1241.

    Article  CAS  Google Scholar 

  7. H. J. Meyer and J. D. Corbett (1991). Inorg. Chem. 30, 963.

    Article  CAS  Google Scholar 

  8. J. Koehler, G. Svensson, and A. Simon (1992). Angew. Chem. Int. Ed. Engl. 31, 1437.

    Article  Google Scholar 

  9. S. Cordier, K. Kirakci, B. Fontaine, J. F. Halet, R. Gautier, and C. Perrin (2006). Inorg. Chem. 45, 883.

    Article  CAS  Google Scholar 

  10. S. Cordier and A. Simon (1999). Solid State Sci. 1, 199.

    Article  CAS  Google Scholar 

  11. S. Cordier, O. Hernandez, and C. Perrin (2001). J. Solid State Chem. 158, 327.

    Article  CAS  Google Scholar 

  12. S. Cordier, O. Hernandez, and C. Perrin (2002). J. Solid State Chem. 163, 319.

    Article  CAS  Google Scholar 

  13. S. Cordier, C. Perrin, and M. Sergent (1997). Mater. Res. Bull. 32, 25.

    Article  CAS  Google Scholar 

  14. S. Cordier, C. Perrin, and M. Sergent (1994). Eur. J. Solid State Inorg. Chem. 31, 1049.

    CAS  Google Scholar 

  15. C. Perrin, S. Cordier, S. Ihmaine, and M. Sergent (1995). J. Alloys Compd. 229, 123.

    Article  CAS  Google Scholar 

  16. S. Cordier, C. Perrin, and M. Sergent (1996). Mater. Res. Bull. 31, 683.

    Article  CAS  Google Scholar 

  17. F. Ogliaro, S. Cordier, J. F. Halet, C. Perrin, J. Y. Saillard, and M. Sergent (1998). Inorg. Chem. 37, 6199.

    Article  CAS  Google Scholar 

  18. S. Cordier, F. Gulo, and C. Perrin (1999). Solid State Sci. 1, 637.

    Article  CAS  Google Scholar 

  19. S. Cordier, F. Gulo, T. Roisnel, R. Gautier, B. le Guennic, J. F. Halet, and C. Perrin (2003). Inorg. Chem. 42, 8320.

    Article  CAS  Google Scholar 

  20. E. V. Anokhina, C. S. Day, M. W. Essig, and A. Lachgar (2000). Angew. Chem. Int. Ed. 39, 1047.

    Article  CAS  Google Scholar 

  21. E. V. Anokhina, M. W. Essig, and A. Lachgar (1998). Angew. Chem. Int. Ed. 37, 522.

    Article  CAS  Google Scholar 

  22. E. V. Anokhina, C. S. Day, and A. Lachgar (2001). Inorg. Chem. 40, 5072.

    Article  CAS  Google Scholar 

  23. N. G. Naumov, S. Cordier, and C. Perrin (2002). Angew. Chem. Int. Ed. 41, 3002.

    Article  CAS  Google Scholar 

  24. M. Sokolov, H. Imoto, T. Saito, and V. Fedorov (1999). Z. Anorg. Allg. Chem. 625, 989.

    Article  CAS  Google Scholar 

  25. Nonius COLLECT, DENZO, SCALEPACK, SORTAV: KappaCCD Program Package (Nonius B.V., Delft, The Netherlands, 1999).

    Google Scholar 

  26. A. Altomare, M. C. Burla, M. Camalli, G. L. Cascarano, C. Giacovazzo, A. Guagliardi, A. G. G. Moliterni, G. Polidori, and R. Spagna (1999). J. Appl. Cryst. 32, 115.

    Article  CAS  Google Scholar 

  27. G. M. Sheldrick SHELX97 release 97–2 (University of Goettingen, Germany, 1997).

    Google Scholar 

  28. N. G. Naumov, S. Cordier, F. Gulo, T. Roisnel, V. E. Fedorov, and C. Perrin (2003). Inorg. Chim. Acta 350, 503.

    Article  CAS  Google Scholar 

  29. N. G. Naumov, S. Cordier, and C. Perrin (2003). Solid State Sci. 5, 1359.

    Article  CAS  Google Scholar 

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Acknowledgments

This work was financially supported by PECO-NEI (contract no. 370) (France). N.G.N. and S·B.A. are gratefully acknowledged Russian Science Support Foundation for financial support.

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Authors and Affiliations

  1. Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences, 3 Acad. Lavrentiev Prosp, 630090, Novosibirsk, Russia

    N. G. Naumov, D. S. Ovoschnikov, D. Y. Naumov, S. B. Artemkina & V. E. Fedorov

  2. Sciences Chimiques de Rennes UMR 6226, CNRS/Université de Rennes1, 263 AVE du Général Leclerc, CS, 74205 35042, Rennes Cedex, France

    S. Cordier & C. Perrin

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  1. N. G. Naumov
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  2. S. Cordier
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  3. D. S. Ovoschnikov
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  4. D. Y. Naumov
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  5. S. B. Artemkina
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  6. C. Perrin
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  7. V. E. Fedorov
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Correspondence to N. G. Naumov.

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Naumov, N.G., Cordier, S., Ovoschnikov, D.S. et al. Octahedral Niobium Thiocyanato Complexes Containing [Nb6Cl9O3] Cluster Core: Syntheses, Crystal Structures and Evidences of NCS Ligand Exchange. J Clust Sci 20, 213–223 (2009). https://doi.org/10.1007/s10876-008-0223-4

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  • DOI: https://doi.org/10.1007/s10876-008-0223-4

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