Abstract
1H NMR spectroscopy was used to study various ligands coordinated to some paramagnetic polyoxometalates (POMs). Pure signals of the complexes were observed, which indicates that ligand exchange is slow on the NMR time scale. Mono- and diprotonated species of [CoW 11 CoO 39 ]8− and [SiW 9 Cu 3 O 37 ]10− were detected from the spectra of pyridine coordinated to these POMs. 2-Aminopyridine binds to [SiW 11 CoO 39 ]6−(SiW 11 Co) whereas 2-methylpyridine does not. This indicates that hydrogen bonding between the amine group and a bridging oxygen atom on SiW 11 Co plays an important role in complex formation. 4- Aminopyrimidine forms two linkage isomers, a and b, binding to SiW 11 Co via N(1) and N(3), respectively. The relative amount of isomer b increases, when D2O is replaced by DMF, indicating that hydrogen bonding between the amine group and SiW 11 Co is more favorable in DMF than in D 2 O. 3,3-Dimethylpiperidine undergoes rapid chair-chair interconversion at room temperature. When it is coordinated to SiW 11 Co in D 2 O the conformation is frozen even at room temperature. When DMSO is added to a D 2 O solution, the spectral change indicates that another conformation is stabilized in DMSO.
This is a preview of subscription content, log in via an institution to check access.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
Preview
Unable to display preview. Download preview PDF.
References
I. Bertini and C. Luchinat: NMR of Paramagnetic Substances, Elsevier, Amsterdam (1996).
J. A. Happe and R. L. Ward: J. Chem. Phys. 39, 1211 (1963).
D. Doddrell and J. D. Roberts: J. Am. Chem. Soc. 92, 6651 (1970).
I. Morishima, T. Yonezawa, and K. Goto: J. Am. Chem. Soc. 92, 6839 (1970).
W. deW. Horrocks, Jr. and D. DeW. Hall: Inorg. Chem. 10, 2368 (1971).
M. Ko, G. I. Rhyu, and H. So: Bull. Korean Chem. Soc. 14, 500 (1993).
L. Banci, I. Bertini, and C. Luchinat: Nuclear and Electron Relaxation, VCH, Weinheim (1991), p 88.
J. Liu, F. Ortega, P. Sethuraman, D. E. Katsoulis, C. E. Costello, and M. T. Pope: J. Chem. Soc. Dalton Trans. 1901 (1992).
H. Y. Woo, H. So, and M. T. Pope: J. Am. Chem. Soc. 118, 621 (1970).
H. Y. Woo, J. Y. Kim, and H. So: Bull. Korean Chem. Soc. 16, 1176 (1995).
D. E. Katsoulis and M. T. Pope: J. Am. Chem. Soc. 106, 737 (1984).
S. H. Szczepankiewicz, C. M. Ippolito, B. P. Santora, T. J. Van de Ven, G. A. Ippolito, L. Fronckowiak, F. Wiatrowski, T. Power, and M. Kozik: Inorg. Chem. 37, 4344 (1998).
M. Ko, G. I. Rhyu, and H. So: Bull. Korean Chem. Soc. 15, 673 (1994).
S. M. Park and H. So: Bull. Korean Chem. Soc. 18, 1002 (1997).
J. Hyun and H. So: Bull. Korean Chem. Soc. 18, 961 (1997).
J. Hyun, S. M. Park, and H. So: Bull. Korean Chem. Soc. 18, 1090 (1997).
B. A. Kim and H. So: Bull. Korean Chem. Soc. 1999 (in press).
V. W. Day and W. G. Klemperer: in Polyoxometalates: From Platonic Solids to Anti-Retroviral Activity, eds. M. T. Pope and A. Müller, Kluwer Academic Publishers, Dordrecht, the Netherlands, p. 100 (1994).
M. M. Mossoba, C. J. O’Connor, M. T. Pope, E. Sinn, G. Hervé, and A. Tézé: J. Am. Chem. Soc. 102, 6866 (1980).
S. P. Harmalker, M. A. Leparulo, and M. T. Pope: J. Am. Chem. Soc. 105, 4286 (1983).
V. W. Day and W. G. Klemperer: Science 228, 533 (1985).
L. Pauling: The Nature of Chemical Bond, Cornell University Press, Ithaca, New York (1960).
M. Barfield and P. Fagerness: J. Am. Chem. Soc. 119, 8699 (1997).
P. O. Lumme: Polyhedron 14, 1553 (1995).
W. H. Knoth, P. J. Domaille and R. L. Harlow: Inorg. Chem. 25, 1577 (1986).
Author information
Authors and Affiliations
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 2001 Kluwer Academic Publishers
About this chapter
Cite this chapter
Kim, B.A., So, H. (2001). NMR Studies of Various Ligands Coordinated to Paramagnetic Polyoxometalates. In: Pope, M.T., Müller, A. (eds) Polyoxometalate Chemistry From Topology via Self-Assembly to Applications. Springer, Dordrecht. https://doi.org/10.1007/0-306-47625-8_13
Download citation
DOI: https://doi.org/10.1007/0-306-47625-8_13
Received:
Publisher Name: Springer, Dordrecht
Print ISBN: 978-0-7923-7011-6
Online ISBN: 978-0-306-47625-9
eBook Packages: Springer Book Archive