Oxovanadium(IV) complexes of phosphonic derivatives of iminodiacetic and nitrilotriacetic acids

Abstract

The complex formation between V^IVO and phosphonic derivatives of iminodiacetic (Ida) and nitrilotriacetic acids (Nta) has been studied by combined application of pH-potentiometric and spectroscopic (EPR and electronic absorption) techniques. Differently from aminomonophosphonates, which are able to bind the metal ion rather weakly forming five-membered chelated rings, the mixed carboxylic–phosphonic and pure phosphonic derivatives of Ida and Nta form chelated systems resulting in very stable complexes mostly of the 1∶1 type. Substitution of CO₂^– by PO₃^2– increases the stability of the complexes due to the higher basicities of the phosphonic functions. However, the higher spatial requirement of the phosphonate groups and the greater electrostatic repulsion between the dinegative phosphonate arms would mostly compensate this effect. Spectroscopic evidence has been found for a considerable distortion in the geometry of the aminophosphonate complexes. The differences in the observed stability trends between the corresponding copper(II) and V^IVO complexes are also discussed.

References

1. T. Kiss, in Biocoordination Chemistry, ed. K. Burger, Ellis Horwood, Chichester, 1990, p. 56 and refs. therein.
2. R. P. Carter, R. L. Carroll and R. R. Irani, Inorg. Chem., 1967, 6, 939.
3. H. E. Lundage Madsen, H. H. Christensen and C. Gottlieb-Petersen, Acta Chem. Scand., Ser. A, 1978, 32, 79.
4. M. Wozniak and G. Nowogrocki, Talanta, 1979, 26, 1135.
5. M. Wozniak and G. Nowogrocki, Talanta, 1979, 26, 381.
6. R. J. Motekaitis and A. E. Martell, Inorg. Chem., 1980, 19, 1646.
7. R. J. Motekaitis and A. E. Martell, J. Coord. Chem., 1985, 14, 139.
8. T. G. Appleton, J. R. Hall and I. J. McMahon, Inorg Chem., 1986, 25, 726.
9. B. Radomska, E. Matczak-Jon and W. Wojciechowski, Inorg. Chim. Acta, 1986, 124, 83.
10. T. Kiss, J. Balla, G. Nagy, H. Kozlowski and J. Kowalik, Inorg. Chim. Acta, 1987, 138, 25.
11. M. A. Dhansay and P. W. Linder, J. Coord. Chem., 1993, 28, 133.
12. T. G. Appleton, K. A. Byriel, J. R. Hall, C. H. L. Kennard, D. E. Lynch, J. A. Sinkinson and G. Smith, Inorg. Chem., 1994, 33, 444 and refs. therein.
13. M. Jezowska-Bojczuk, T. Kiss, H. Kozlowski, P. Decock and J. Barycki, J. Chem. Soc., Dalton Trans., 1994, 811.
14. K. Wüthrich, Helv. Chim. Acta, 1965, 48, 779.
15. A. Napoli and L. Pontelli, Gazz. Chim. Ital., 1973, 103, 1219.
16. A. Napoli, J. Inorg. Nucl. Chem., 1977, 39, 463.
17. J. Felcman and J. J. R. Fraúst da Silva, Talanta, 1983, 30, 565.
18. M. Nishizawa, Y. Sasaki and K. Saito, Inorg. Chem., 1985, 24, 767.
19. R. Meier, G. Werner and M. Otto, Collect. Czech. Chem. Commun., 1989, 54, 64.
20. E. Alberico, G. Micera, D. Sanna and A. Dessì, Polyhedron, 1994, 13, 1763.
21. G. Gran, Acta Chem. Scand., 1950, 4, 559.
22. I. Nagypál and I. Fábián, Inorg. Chim. Acta, 1982, 61, 109.
23. H. Irving, M. G. Miles and L. D. Pettit, Anal. Chim. Acta, 1967, 38, 475.
24. L. Zékány and I. Nagypál, in Computational Methods for the Determination of Stability Constants, ed. D. Leggett, Plenum, New York, 1985.
25. R. P. Henry, P. C. H. Mitchell and J. E. Prue, J. Chem. Soc., Dalton Trans., 1973, 1156.
26. A. Komura, M. Hayashi and H. Imanaga, Bull. Chem. Soc. Jpn., 1977, 50, 2927.
27. T. Kiss, E. Kiss, G. Micera and D. Sanna, Inorg. Chim. Acta, 1998, 283, 202.
28. M. Wozniak and G. Nowogrocki, Talanta, 1978, 25, 633.
29. D. Sanna, G. Micera, P. Buglyò and T. Kiss, J. Chem. Soc., Dalton Trans., 1996, 87.
30. D. Wauchope, J. Agric. Food. Chem., 1976, 24, 717.
31. I. Fábián and I. Nagypál, Inorg. Chim. Acta, 1982, 62, 193.
32. V. P. Vasil'ev, M. V. Kumurov, L. A. Kochergina and N. V. Tsirul'nikova, Zh. Obshch. Khim., 1983, 53, 1990.
33. P. Buglyò, N. Culeddu, T. Kiss, G. Micera and D. Sanna, J. Inorg. Biochem., 1995, 60, 45.
34. T. D. Smith, J. F. Boas and J. R. Pilbrow, Aust. J. Chem., 1974, 27, 2535.
35. K. W. H. Stevens, Proc. R. Soc. London, Ser. A, 1952, 214, 237.
36. C. J. Ballhausen and H. B. Gray, Inorg. Chem., 1962, 1, 111.
37. N. D. Chasteen and R. L. Belford, Inorg. Chem., 1969, 8, 408.
38. L. D. Pettit and H. K. J. Powell, Stability Constant Database, Academic Software-IUPAC, London, 1993.
39. S. H. Whitlow, Inorg. Chem., 1973, 10, 2286.