Skip to main content
SpringerLink
Log in

Characterization and Equilibrium of Beryllium(II) Solvates [BeSn(H2O)4-n]2+(n=0-4, S=N,N-Dimethylformamide and 1,1,3,3-Tetramethylurea) studied by 9Be NMR Spectroscopy

  • Original Paper
  • Published:
Analytical Sciences Aims and scope Submit manuscript

Abstract

Beryllium(II) solvates [BeSnH2O)4-n]2+ (H=0 - 4, S=N, N-dimethylformamide (dmf) and 1,1,3,3-tetramethyrorea (tmu)) in acetonitrile have been characterized by ’Be NMR spectroscopy. The difference in steric effects of the bound dmf and tmu molecules on the structures of the solvates has been clarified by ’Be NMR chemical shifts. The stepwise formation constants, A),=[[BeSn(H2O)4-n]2+][H2O][[BeSn-1(H2O)5-n]2+]-1[S]-1 (n =1-4), obtained from the 9Be NMR signal intensities for the tmu system drastically decrease between K1 and K2 and between K3 and K4, while those for the dmf system decrease statistically with an increase in n. Such a difference in the stability of the two systems is discussed in connection with the steric effects

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. R. G. Wilkins, “The Study of Kinetics and Mechanism of Reactions of Transition Metal Complexes”, Allyn and Bacon, Boston, 1974.

    Google Scholar 

  2. J. Burgess, “Metal Ions in Solution”, Ellis Horwood, New York, 1978.

    Google Scholar 

  3. B. Lindman and S. Fors’en, “NMR and the Periodic Table”, ed. R. K. Harris and B. E. Mann, pp. 129–194, Academic Press, New York, 1978.

  4. A.I. Popov, Pure Appll. Chem., 41, 275 (1975).

    Article  CAS  Google Scholar 

  5. W. J. De Witte, R. C. Schoening and A. I. Popov, Inorg. Nucl. Chem. Lett., 12, 251 (1976).

    Article  Google Scholar 

  6. J. S. Shih and A. I. Popov, Inorg. Nucl. Chem. Lett., 13, 105 (1977).

    Article  Google Scholar 

  7. R. H. Erlich, E. Roach and A. I. Popov, J. Am. Chem. Soc, 92, 4989 (1970).

    Article  CAS  Google Scholar 

  8. R. H. Erlich and A. I. Popov, J. Am. Chem. Soc., 93, 5620 (1971).

    Article  CAS  Google Scholar 

  9. P.-A. Pittet, G. Elbaze, L. Helm and A. E. Merbach, Inorg. Chem., 29, 1936 (1990).

    Article  CAS  Google Scholar 

  10. J. Frahn and H.-H. Füldner, Ber. Bunsen-Ges. Phys. Chem., 84, 173 (1980).

    Article  Google Scholar 

  11. R. F. Connick and D. N. Fiat, J. Chem. Phys., 39, 1349 (1963).

    Article  CAS  Google Scholar 

  12. T. Yamaguchi, H. Ohtaki, E. Spohr, G. Pâlink’as, K. Heinzinger and M. M. Probst, Z. Naturforsch., A41, 1175 (1986).

    Article  Google Scholar 

  13. I. G. Dance and H. C. Freeman, Acta Crystallogr., B25, 304 (1969).

    Article  CAS  Google Scholar 

  14. S. K. Sikka and R. Chidambaram, Acta Crystallogr., B25, 310 (1969).

    Article  Google Scholar 

  15. R. D. Shannon, Acta Crystallogr., A32, 751 (1976).

    Article  CAS  Google Scholar 

  16. The chemical shift for each signal is independent of the concentration of the beryllium(II) ion and temperature. Small signals 2 in spectrum a and 2′ in spectrum e are attributed to the strong affinity of the beryllium(H) ion with water which results in difficulty in complete dehydration of the dmf and tmu solvates.

  17. K. Gutmann, “The Donor-Acceptor Approach to Molecular Interaction”, Plenum Press, New York, 1978.

    Book  Google Scholar 

  18. The Gutmann donor number of water is 18, while the donor number estimated by the 23Na NMR chemical shift is ca. 33.

  19. The shielding for the 23Na nucleus in the corresponding solvents increases in the order, dmf<tmu<H2O.

  20. If the probability of the replacement of water by dmf and that of dmf by water depends on the numbers of the applicable substitution sites in each species, the ratios of the stepwise formation constants K1: K2: K3: K4 become 48:18:8:3 statistically.

  21. A. E. Merbach, Pure Appl Chem., 59, 161 (1987).

    Article  CAS  Google Scholar 

  22. M. Inamo, K. Ishihara, S. Funahashi, Y. Ducommun, A. E. Merbach and M. Tanaka, Inorg. Chem., 30, 1580 (1991).

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Laboratory of Analytical Chemistry, Faculty of Engineering, Shizuoka University, Johoku, Hamamatsu, 432, Japan

    Sen-ichi Aizawa

  2. Laboratory of Analytical Chemistry, Faculty of Science, Nagoya University, Nagoya, 464-01, Japan

    Tadahiko Kato & Shigenobu Funahashi

Authors
  1. Sen-ichi Aizawa
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Tadahiko Kato
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Shigenobu Funahashi
    View author publications

    You can also search for this author in PubMed Google Scholar

Rights and permissions

Reprints and permissions

About this article

Cite this article

Aizawa, Si., Kato, T. & Funahashi, S. Characterization and Equilibrium of Beryllium(II) Solvates [BeSn(H2O)4-n]2+(n=0-4, S=N,N-Dimethylformamide and 1,1,3,3-Tetramethylurea) studied by 9Be NMR Spectroscopy. ANAL. SCI. 13, 541–544 (1997). https://doi.org/10.2116/analsci.13.541

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.2116/analsci.13.541

Keywords

Search

Navigation