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Functionalization of polyoxomolybdates: the example of nitrosyl derivatives

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Molecular Engineering

Abstract

Nitrosyl derivatives of polyoxomolybdates have been synthesized and characterized by X-ray diffraction. Most of them contain the MoII(NO)3+ unit and their structures are related to the following structural types: Lindqvist, Keggin and decatungstate [W10O32]4−. Reductive nitrosylation of (NBu4)4[α-Mo8O26] by hydroxylamine in methanol yields (NBu4)2[Mo5O13(OMe)4(NO){Na(MeOH)}]. 3MeOH, which is a versatile reagent yielding a variety of derivatives (i) by the transformation of [Mo5O13(OMe)4(NO)]3− into [Mo6O18(NO)]3− in acetonitrile, (ii) by the formation of [PMo12O39(NO)]4− by reaction of [Mo5O13(OMe)4(NO)]3− with [PMO12O40]3− in basic condition and (iii) by the formation of mixed valence MoVI/MoV/MoII decamolybdates [Mo10O24(OMe)7(NO)]2−, [Mo10O25(OMe)6(NO)]− and [Mo10O20(OMe)9(NO)3]2− by chemical reduction of [Mo5O13(OMe)4(NO)]3−; MoII is localized while MoV are delocalized in the first two species but localized in the third. The unique ligating properties of [Mo5O13(OMe)4(NO)]3− have been documented: this species acts as a tetradentate ligand in [Ce{Mo5O13(OMe)4(NO)}2]2−, a symmetrically tetraligating ligand in [Rh2Cp*2(μ-Br){μ-Mo5O13(OMe)4(NO)}] and a bidentate ligand in [Mo5O13(OMe)4(NO){RhCp*(H2O)}]−. Some polyoxomolybdates of the type [Mo5(NO)2O12{RC(NH2)NHO}2{RC(NH)NO}2]2−, which contain the Mo0(NO) 2+2 unit, have also been characterized.

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References

  1. M. T. Pope:Heteropoly and Isopoly Oxometalates, Springer-Verlag, Berlin, Heidelberg (1983); V. W. Day and W. G. Klemperer:Science 228, 533 (1985); M. T. Pope and A. Müller:Angew. Chem. Int. Ed. Engl. 30, 34 (1991); Q. Chen and J. Zubieta:Coord. Chem. Rev. 114, 107 (1992).

    Google Scholar 

  2. E. M. McCarron, H. H. Staley, and W. Sleight:Inorg. Chem. 23, 1043 (1984); E. M. McCarron and R. L. Harlow:J. Am. Chem. Soc. 105, 6179 (1983); H. Kang, S. Liu, S. N. Shaikh, T. Nicholson, and J. Zubieta:Inorg. Chem. 28, 920 (1989); Q. Chen, L. Ma, S. Liu, and J. Zubieta,J. Am. Chem. Soc. 111, 5944 (1989).

    Google Scholar 

  3. A. J. Wilson, W. T. Robinson, and C. J. Wilkins:Acta Cryst. C39, 54 (1983); L. Ma, S. Liu, and J. Zubieta:Inorg. Chem. 28, 175 (1989); S. Liu, L. Ma, D. McGowty, and J. Zubieta,Polyhedron 9, 1541 (1990); Q. Chen and J. Zubieta:Inorg. Chem. 29, 1458 (1990); M. I. Khan, Q. Chen, and J. Zubieta,J. Chem. Soc., Chem. Commun. 305 (1992); M. I. Khan, Q. Chen, P. Goshorn, H. Hope, S. Parkin, and J. Zubieta,J. Am. Chem. Soc. 114, 3341 (1992); Q. Chen and J. Zubieta:Inorg. Chem. 31, 1556 (1992).

    Google Scholar 

  4. R. Adams, W. G. Klemperer, and R.-S. Liu:J. Chem. Soc., Chem. Commun. 256 (1979).

  5. V. W. Day, M. F. Fredrich, W. G. Klemperer, and R.-S. Liu,J. Am. Chem. Soc. 101, 491 (1979);102, 5971 (1980); Q. Chen, S. Liu, H. Zhu, and J. Zubieta,Polyhedron 8, 2915 (1989).

    Google Scholar 

  6. S. N. Shaikh and J. Zubieta:Inorg. Chem. 25, 4613 (1986); H. Kang and J. Zubieta:J. Chem. Soc., Chem. Commun. 1192 (1988).

    Google Scholar 

  7. T.-C. Hsieh and J. Zubieta:Inorg. Chem. 24, 1287 (1985); T.-C. Hsieh and J. Zubieta:Polyhedron 5, 1655 (1986); Q. Chen, S. Liu, and J. Zubieta:Inorg. Chim. Acta 164, 115 (1989); S. Bank, S. Liu, S. N. Shaikh, X. Sun, J. Zubieta, and P. D. Ellis:Inorg. Chem. 27, 3535 (1988).

    Google Scholar 

  8. Y. H. Du, A. L. Rheingold, and E. A. Maatta:J. Am. Chem. Soc. 114, 345 (1992).

    Google Scholar 

  9. E. M. McCarron, J. F. Whitney, and D. B. Chase:Inorg. Chem. 23, 3275 (1984).

    Google Scholar 

  10. J. R. Harper and A. L. Rheingold:J. Am. Chem. Soc. 112, 4037 (1990).

    Google Scholar 

  11. H. K. Chae, W. G. Klemperer, and V. W. Day:Inorg. Chem. 28, 1424 (1989); Y. Hayashi, Y. Ozawa, and K. Isobe:Chem. Lett. 425 (1989);Inorg. Chem. 30, 1025 (1991).

    Google Scholar 

  12. C. J. Besecker and W. G. Klemperer:J. Am. Chem. Soc. 102, 7598 (1980); C. J. Besecker, V. W. Day, W. G. Klemperer, and M. R. Thompson:Inorg. Chem. 27, 44 (1985); C. J. Besecker, V. W. Day, W. G. Klemperer, and M. R. Thompson:J. Am. Chem. Soc. 106, 4125 (1984); C. J. Besecker and W. G. Klemperer:J. Am. Chem. Soc. 102, 7598 (1982); C. J. Besecker, W. G. Klemperer, and V. W. Day:J. Am. Chem. Soc. 104, 6158 (1982); W. G. Klemperer and D. J. Main:Inorg. Chem. 29, 2355 (1990); V. W. Day, W. G. Klemperer, and D. J. Main:Inorg. Chem. 29, 2345 (1990).

    Google Scholar 

  13. V. W. Day, W. G. Klemperer, and D. J. Maltbie:Organometallics 4, 104 (1985).

    Google Scholar 

  14. V. W. Day, C. W. Earley, and W. G. Klemperer:J. Am. Chem. Soc. 107, 8261 (1985).

    Google Scholar 

  15. V. W. Day, M. F. Fredrich, M. R. Thompson, W. G. Klemperer, R. S. Liu, and W. Shum:J. Am. Chem. Soc. 103, 3597 (1981).

    Google Scholar 

  16. R. G. Finke and M. W. Droege:J. Am. Chem. Soc. 106, 7274 (1984); R. G. Finke, B. Rapko, and P. J. Domaille:Organometallics 5, 175 (1986).

    Google Scholar 

  17. D. J. Edlung, R. J. Saxton, D. K. Lyon, and R. G. Finke:Organometallics 7, 1692 (1988); R. G. Finke, D. K. Lyon, K. Nomiyo, S. Sur, and N. Mizuno:Inorg. Chem. 29, 1784 (1990).

    Google Scholar 

  18. V. W. Day, W. G. Klemperer, and A. Yagasaki:Chem. Lett. 1267 (1990).

  19. Y. Hayashi, K. Toriumi, and K. Isobe:J. Am. Chem. Soc. 110, 3666 (1988); Y. Do, X. Z. You, C. Zhang, Y. Ozawa, and K. Isobe:J. Am. Chem. Soc. 113, 5892 (1991).

    Google Scholar 

  20. A. R. Siedle, C. G. Markell, P. A. Lyon, K. O. Hodgson, and A. L. Roe:Inorg. Chem. 26, 219 (1987).

    Google Scholar 

  21. P. Gouzerh, Y. Jeannin, A. Proust, and F. Robert:Angew. Chem., Int. Ed. Engl. 28, 1363 (1989).

    Google Scholar 

  22. A. Proust: Thesis 1992, Univ. P. et M. Curie, Paris, France.

  23. S. G. Roh: Thesis in preparation, Univ. P. et M. Curie, Paris, France.

  24. M. N. Hughes:The Inorganic Chemistry of Biological Processes, Wiley, New York, 188 (1981).

    Google Scholar 

  25. D. Sellmann and B. Seubert:Angew. Chem. Int. Ed. Engl. 31, 205 (1992).

    Google Scholar 

  26. S. K. Ibrahim and C. J. Pickett:J. Chem. Soc., Chem. Commun. 246 (1991).

  27. K. K. Pandey:Coord. Chem. Rev. 51, 69 (1983).

    Google Scholar 

  28. J. O. Dziegielewski, K. Filipek, and B. Jezowska-Trzebiatowska:Polyhedron 10, 429 (1991).

    Google Scholar 

  29. L. I. Kuznetsova, M. A. Fedotov, L. G. Detusheva, and E. N. Yurchenko:Proceedings of the XXVIII Int. Conf. Coord. Chem., Gera 3 (1990).

  30. M. A. Andrews, T. C. T. Chang, and C. W. F. Cheng:Organometallics 4, 268 (1985); M. M. T. Khan, K. Venkatasubramanian, Z. Shirin, and M. M. Bhadbhade:J. Chem. Soc., Dalton Trans. 1031 (1992).

    Google Scholar 

  31. D. Sutton:Chem. Soc. Rev. 4, 443 (1975).

    Google Scholar 

  32. S. Zhang, D. Liao, M. Shao, and Y. Tang:J. Chem. Soc., Chem. Commun. 835 (1986).

  33. K. G. Caulton:Coord. Chem. Rev. 14, 317 (1975); J. H. Enemark and R. D. Feltham:Coord. Chem. Rev. 13, 339 (1974); D. M. P. Mingos and D. J. Sherman:Adv. Inorg. Chem. 34, 293 (1989); B. F. G. Johnson, B. L. Haymore, and J. R. Dilworth:Comprehensive Coordination Chemistry, eds. G. Wilkinson, R. D. Gillard, and J. A. McCleverty, Pergamon Press, Oxford,2, 13. 3, 99 (1987); G. B. Richter-Addo and P. Legzdins:Chem. Rev. 88, 891 (1988); J. A. McCleverty:Chem. Rev. 79, 53 (1979); F. Bottomley:Reactions of Coordinated Ligands, ed. P. S. Braterman, Plenum Press, New York,2, 3, 115 (1989).

    Google Scholar 

  34. V. Chilou, P. Gouzerh, Y. Jeannin, and C. B. Knobler:Inorg. Chim. Acta 178, 23 (1990).

    Google Scholar 

  35. S. Sarkar and A. Müller:Z. Naturforsch. Teil B 33 1053 (1978); S. Sarkar and A. Müller:Ang. Chem. Int. Ed. 16 183 (1977); A. Müller, U. Seyer, and W. Eltzner:Inorg. Chim. Acta 32, L65 (1979); A. Müller, W. Eltzner, and N. Mohan:Ang. Chem. Int. Ed. Engl. 18, 168 (1979); A. Müller, S. Sarkar, N. Mohan, and R. G. Bhattacharyya:Inorg. Chim. Acta 45, L245 (1980); A. Müller and N. Mohan:Z. Anorg. Allg. Chem. 480, 157 (1980); A. Müller, N. Mohan, S. Sarkar, and W. Eltzner:Inorg. Chim. Acta 55, L33 (1981); A. Müller, W. Eltzner, H. Bogge, and S. Sarkar:Ang. Chem. Int. Ed. Engl. 21, 535 (1982); A. Müller, W. Eltzner, H. Bogge, and E. Krickemeyer:Ang. Chem. Int. Ed. Engl. 22, 884 (1983).

    Google Scholar 

  36. K. Wieghardt, W. Holzbach, J. Weiss, B. Nuber, and B. Prikner:Angew. Chem., Int. Ed. Engl. 18, 548 (1979); K. Wieghardt, and W. Holzbach:Angew. Chem., Int. Ed. Engl. 18, 549 (1979); K. Wieghardt, W. Holzbach, B. Nuber, and J. Weiss:Chem. Ber. 113, 629 (1980); K. Wieghardt, G. Backes-Dahmann, W. Swiridoff, and J. Weiss:Inorg. Chem. 22, 1221 (1983).

    Google Scholar 

  37. K. Wieghardt:Adv. Inorg. Chem. Bioinorg. Mech. 3, 213 (1984).

    Google Scholar 

  38. N. H. Hur, W. G. Klemperer, and R.-C. Wang:Inorganic Syntheses, Wiley27, 77–79 (1990); B. Krebs and I. Paulat-Böschen:Acta Cryst., Sec. B 38, 1710 (1982).

  39. J. Iball, J. N. Low, and T. J. R. Weakley:J. Chem. Soc., Dalton Trans. 2021 (1974).

  40. A. M. Golubev, L. A. Murandyan, L. P. Kazanskii, E. A. Torchenkova, V. I. Simonov, and V. I. Spitsyn:J. Coord. Chem. (Engl. Transl.) 3, 715 (1977).

    Google Scholar 

  41. J. Fuchs, H. Hartl, W. Schiller, and U. Gerlach:Acta Cryst. B32, 740 (1975).

    Google Scholar 

  42. S. Liu and J. Zubieta:Polyhedron 8, 537 (1989); H. Kang, S. Liu, S. N. Shaikh, T. Nicholson, and J. Zubieta:Inorg. Chem. 28, 920 (1989); Q. Chen, S. Liu, and J. Zubieta:Inorg. Chim. Acta 164, 115 (1989).

    Google Scholar 

  43. P. T. Meiklejohn, M. T. Pope, and R. A. Prados:J. Am. Chem. Soc. 96, 6779 (1974).

    Google Scholar 

  44. S. Sarkar and P. Subramanian:Inorg. Chim. Acta 35, L357 (1979).

    Google Scholar 

  45. V. Chilou, P. Gouzerh, Y. Jeannin, and F. Robert:J. Chem. Soc., Chem. Comm. 76 (1989).

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  1. Laboratoire de Chimie des Métaux de Transition, URA-CNRS 419, Université Pierre et Marie Curie, 4 Place Jussieu, 75252, Paris Cedex 05, France

    P. Gouzerh, Y. Jeannin, A. Proust, F. Robert & S. G. Roh

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Gouzerh, P., Jeannin, Y., Proust, A. et al. Functionalization of polyoxomolybdates: the example of nitrosyl derivatives. Mol Eng 3, 79–91 (1993). https://doi.org/10.1007/BF00999625

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