Application of electrospray ionisation mass spectrometry to the study of dilute aqueous oligomeric anions and their reactions

Abstract

For the first time, electrospray ionisation mass spectrometry has been carried out on purely aqueous solutions of anions, specifically dilute (10^–3 mol dm^–3) isopolytungstates, peroxotungstates and heteropolymolybdates and tungstates. Many new species have been detected that have not previously been reported in water, including [W₆O₁₉]^2– and [W₂O₇]^2–. To demonstrate its investigative potential, the method was used to identify the complex and previously uncharacterised reaction products from the reaction of H₂O₂ on powdered tungsten metal, where hexametalates form with up to four peroxo ligands, and also to track kinetic processes such as the course of metal-ion exchange between phosphododecametalates, and the attack of H₂O₂ on paratungstate B.

References

1. M. T. Pope and A. Müller, Polyoxometalates: From Platonic Solids to Anti-Retroviral Activity, Kluwer, Dordrecht, 1994, (a)p. 255, (b)p. 267, (c)p. 281, (d)p. 307, (e)p. 315 and (f)p. 327.
2. M. Raynaud, J. C. Chermann, F. Plata, C. Jasmin and G. Mathé, C. R. Acad. Sci. Paris, 1971, 272, 347.
3. P. V. Ashrit, F. E. Girouard and V. V. Truong, Solid State Ionics, 1996, 89, 65.
4. J. C. Valmalette and J. R. Gavarri, Sol. Energy Mater. Sol. Cells, 1994, 33, 135.
5. K. A. Khan and M. S. R. Khan, Paramana J. Phys., 1992, 38, 389.
6. N. H. Youseff and M. A. Amer, Astron. Astrosphys., 1989, 209, 391.
7. I. A. Weinstock, R. H. Atalla, U. P. Agarwal, J. L. Minor and C. Petty, Spectrochim. Acta, Part A, 1993, 49, 819.
8. I. A. Weinstock, R. H. Atalla, R. S. Reiner, M. A. Moen, K. E. Hammel, C. J. Houtman and C. L. Hill, New J. Chem., 1996, 20, 269.
9. R. G. Finke, M. W. Droege, J. C. Cook and K. S. Suslick, J. Am. Chem. Soc., 1984, 106, 5750.
10. R. G. Finke, B. Rapko, R. J. Saxton and P. J. Domaille, J. Am. Chem. Soc., 1986, 108, 2947.
11. A. Trovarelli and R. G. Finke, Inorg. Chem., 1993, 32, 6034.
12. T. C. Lau, J. Wang, K. W. M. Siu and R. Guevremont, J. Chem. Soc., Chem. Commun., 1994, 1487.
13. J. Le Quan Tuoi and E. Muller, Rapid Commun. Mass Spectrom., 1994, 8, 692.
14. T. C. Lau, J. Wang, R. Guevremont and K. W. M. Siu, J. Chem. Soc., Chem. Commun., 1995, 877.
15. M. T. Pope, Heteropoly and Isopoly Oxometalates, Springer, Berlin, 1983, p. 51.
16. O. W. Howarth and J. J. Hastings, J. Chem. Soc., Dalton Trans., 1992, 209.
17. T. Kudo, J. Oi, A. Kishimoto and M. Hiratani, Mater. Res. Bull., 1991, 26, 779.
18. R. I. Maksimovskaya, S. M. Maksimov, A. A. Blokhin and V. P. Taushkanov, Russ. J. Inorg. Chem. (Engl. Transl.), 1991, 4, 36.
19. I. Andersson, J. J. Hastings, O. W. Howarth and L. Pettersson, J. Chem. Soc., Dalton Trans., 1994, 1061.
20. O. Bortolini and P. Traldi, J. Organomet. Chem., 1989, 379, C13.
21. A. D. Westland, F. Haque and J. M. Bouchard, Inorg. Chem., 1980, 19, 2255.
22. H. Mimoun, J. Mol. Catal., 1980, 7, 1.
23. A. D. Westland and M. T. H. Tarafdler, Inorg. Chem., 1982, 21, 3228.
24. M. T. H. Tarafdler and A. R. Khan, Polyhedron, 1987, 6, 275.
25. M. T. H. Tarafdler and A. Ahmed, Indian J. Chem., Sect. A, 1986, 25, 729.
26. M. S. Islam and M. M. Uddin, Polyhedron, 1992, 11, 2913.
27. M. S. Sastry and S. S. Gupta, Transition Met. Chem. (Weinheim, Ger.), 1996, 21, 410.