Formation of a novel µ₃-borate-capped triniobium cluster via hydrolysis of a hydridotris(pyrazol-1-yl)borate ligand

Abstract

The novel µ₃-hydroxotrioxoborato-capped cluster [Nb₃{µ₃-BO₃(OH)}(µ-O)₃{HB(pz)₃}₃] 1 has been obtained following evaporation to dryness of aqueous HCl solutions of [Nb₃(µ₃-Cl)(µ-O)₃(OH₂)₉]⁴⁺ and treatment with ethanolic potassium hydridotris(pyrazol-1-yl)borate, K[HB(pz)₃]. The capping borate group derives from hydrolysis of a HB(pz)₃^– ligand in the presence of the aqua precursor. Air oxidation of 1 results in complete fragmentation, loss of the borate cap and reassembly in the form of a rectangular tetranuclear oxo-bridged product.

References

1. S. Minhas and D. T. Richens, J. Chem. Soc., Dalton Trans., 1996, 703.
2. F. A. Cotton, M. P. Diebold, R. Llusar and W. J. Roth, J. Chem. Soc., Chem. Commun., 1986, 1276.
3. B.-L. Ooi, T. Shibahara, G. Sakane and K.-F. Mok, Inorg. Chim. Acta, 1997, 266, 103.
4. D. T. Richens and I. J. Shannon, unpublished work.
5. SIR 92, A. Altomare, G. Cascarano, C. Giacovazzo and A. Guagliardi, J. Appl. Crystallogr., 1994, 27, 1045; A. Altomare, C. Giacovazzo and A. Moliterni, Acta Crystallogr., Sect. A, 1994, 50, 585.
6. DIRDIF 94, P. T. Beurskens, G. Admiraal, G. Beurskens, W. P. Bosman, R. de Gelder, R. Israel and J. M. M. Smits, Technical Report of the Crystallographic Laboratory, University of Nijmegen, 1994; C. Smykalla, P. T. Beurskens, W. P. Bosman and S. Garciagranda, J. Appl. Crystallogr., 1994, 27, 661.
7. D. T. Cromer and J. T. Waber, in International Tables for X-Ray Crystallography, Kynoch Press, Birmingham, 1974, vol. 4, Table 2.2A.
8. J. A. Ibers and W. C. Hamilton, Acta Crystallogr., 1964, 17, 781.
9. TEXSAN, Crystal Structure Analysis Package, Molecular Structure Corporation, Houston, TX, 1985 and 1992.
10. A. Simon and H. G. von Schnering, Z. Anorg. Allg. Chem., 1965, 339, 155.
11. F. Bottomley and S. Karslioglu, J. Chem. Soc., Chem. Commun., 1991, 222.
12. F. A. Cotton, M. P. Diebold, X. Feng and W. J. Roth, Inorg. Chem., 1988, 27, 3414.
13. (a) F. A. Cotton, M. P. Diebold and W. J. Roth, Inorg. Chem., 1988, 27, 2347; (b) F. A. Cotton, S. A. Duraj and W. J. Roth, J. Am. Chem. Soc., 1984, 106, 3527.
14. A. Bino, Inorg. Chem., 1982, 21, 1917.
15. V. T. Kalinnikov, A. A. Pasynskii, G. M. Larin, V. M. Novotortsev, Yu. T. Struchkov, A. I. Gusev and N. I. Kirillova, J. Organomet. Chem., 1974, 74, 91.
16. I. D. Brown and D. Altermatt, Acta Crystallogr., Sect B, 1985, 41, 244.
17. J. O. Edwards and V. F. Ross, in The chemistry of boron and its compounds, ed. E. L. Muetterties, Wiley, New York, 1967, ch. 3, pp. 155–207.
18. F. Bottomley, Organometallics, 1993, 12, 2652.
19. F. Bottomley and R. W. Day, Organometallics, 1991, 10, 2560.
20. F. Bottomley, J. Chen, K. F. Preston and R. C. Thompson, J. Am. Chem. Soc., 1994, 116, 7989.
21. J. R. Harper and A. L. Rheingold, J. Am. Chem. Soc., 1990, 112, 4037.
22. E. J. Graeber and B. Morosin, Acta Crystallogr., Sect B, 1977, 33, 2137.
23. C. M. Flynn and G. O. Stuckey, Inorg. Chem., 1969, 8, 335.
24. C. Chavant, J. C. Daran, Y. Jeannin, G. Constant and R. Moracho, Acta Crystallogr., Sect. B, 1975, 31, 1828.
25. C. Djordjevic and V. Katovic, Chem. Commun., 1966, 224; J. Chem. Soc. A, 1970, 3382; V. Katovic and C. Djordjevic, Inorg. Chem., 1970, 9, 1720.
26. J. C. Dewan, D. L. Kepert, C. L. Raston and A. H. White, J. Chem. Soc., Dalton Trans., 1975, 2031.
27. J. D. Wilkins, J. Organomet. Chem., 1974, 80, 349.
28. G. Mathern, R. Weiss and R. Rohmer, Chem. Commun., 1969, 70.
29. M. Galesic, B. Markovic, M. Herceg and M. Sljukic, J. Less Commun. Met., 1971, 25, 234.
30. B. Kojic-Prodic, R. Livinga and S. Scavnicar, Acta Crystallogr., Sect. B, 1973, 29, 864.
31. L. G. Hubert-Pfalzgraf and J. G. Riess, Inorg. Chim. Acta, 1980, 47, 7.