Mixed-Valence Chemistry of Adjacent Vanadium Centers in Heteropolytungstate Anions. 1. Synthesis and Electronic Structures of Mono-, Di-, and Trisubstituted Derivatives of α-[P2W18O62]6-

Journal of the American Chemical Society

Volumn 105, Issue 13, 1983, Pages 4286-4292

  Harmalker, Subhash P ^a   Leparulo, Michele A ^a   Pope, Michael T ^a  

^a GEORGETOWN UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

TUNGSTEN COMPOUNDS;

IONS;

EID: 0020765376     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja00351a028     Document Type: Article

References (47)

1. From the Ph.D. Theses of S.P.H. (Georgetown University, 1982) and M.A.L. (Georgetown University, in preparation). A preliminary account of some of this work has been published: Harmalker, S. P.; Pope M. T. J. Am. Chem. Soc. 1981, 103, 7381.
2. Robin M. B.; Day, P. Adv. Inorg. Chem. Radiochem. 1967, 10, 247.
3. Day, P. Int. Rev. Phys. Chem. 1981, 1, 149.
4. Prados R. A.; Pope M. T. Inorg. Chem. 1976, 15, 2547.
5. Che M.; Fournier M.; Launay J. P. J. Chem. Phys. 1979, 71, 1954.
6. Launay J. P.; Fournier M.; Sanchez C; Livage J.; Pope, M. T. Inorg. Nucl. Chem. Lett. 1980, 16, 257.
7. Sanchez, C.; Livage J.; Launay J. P.; Fournier M.; Jeannin Y. J. Am. Chem. Soc. 1982, 104, 3194.
8. Hush, N. S. Prog. lnorg. Chem. 1967, 8, 391.
9. “Mixed-Valence Compounds” Brown D. B., Ed.; D. Reidel: Dordrecht, 1980; p 151.
10. Piepho S. B.; Krausz E. R.; Schatz, P. N. J. Am. Chem. Soc, 1978, 100, 2996.
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13. Several examples are given in “Mixed-Valence Compounds” Brown D. B., Ed.; D. Reidel, Dordrecht, 1980.
14. Contant R.; Ciabrini, J. P. J. Chem. Res., Synop. 1977, 222;
15. J. Chem. Res. Miniprint 2601.
16. Flynn C. M. Jr., Pope, M. T. Inorg. Chem. 1971, 10, 2524.
17. Erdey, L. “Gravimetric Analysis” Pergamon Press: Oxford, 1965; Vol. II.
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19. Prados R. A.; Pope M. T. Inorg. Chem. 1976, 15, 2547.
20. Venables J.; Brill, A. S. University of Virginia, private communication.
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28. Kato R.; Kobayashi A.; Sasaki Y. Inorg. Chem. 1982, 21, 240.
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33. Smith D. P.; So H.; Bender J.; Pope M. T. Inorg. Chem. 1973, 12, 685.
34. DeArmond K.; Garrett B. B.; Gutowsky H. S. J. Chem. Phys. 1965, 42, 1019.
35. At lower temperatures the lines broaden as a result of slow molecular tumbling, see: Harmalker, S. P.; Pope M. T. J. Phys. Chem. 1978, 82, 2823.
36. In view of the lower oxidation state of vanadium vis-á-vis tungsten, these oxygen atoms are expected to be the most basic sites on the surface of the heteropolyanion. This conclusion is strengthened by 17O NMR results which indicate that the V-O-V oxygen atom is protonated in acetonitrile solutions of HV2W4O193- (Klemperer, W. G.; Shum, W. J. Am. Chem. Soc. 1978, 100, 4891).
37. Cannon, R. D. “Electron Transfer Reactions” Butterworths: London 1980.
38. Meyer T. J., ref 6, p 75.
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40. Powers M. J.; Meyer T. J. J. Am. Chem. Soc. 1978, 100, 4393; 1980, 102, 1289.
41. Barcza L.; Pope M. T. J. Phys. Chem. 1975, 79, 92.
42. Meyer, T. J. Chem. Phys. Lett. 1979, 64, 417.
43. Brunschwig B. S.; Logan J.; Newton M. D.; Sutin N. J. Am. Chem. Soc. 1980, 102, 5798.
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45. Launay J. P.; Babonneau, F. Chem. Phys. 1982, 67, 295.
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47. Sanchez, C.; Michaud M.; Livage J.; Hervè, G., J. Inorg. Nude. Chem. 1981, 43, 2795.