Stabilization of High Oxidation States in Transition Metals. 2.1 WClWCl6 Oxidizes [WF6]-, but Would PtCl6 Oxidize [PtF6]-? An Electrochemical and Computational Study of 5d Transition Metal Halides: [MF6]Z versus [MCl6]Z (M = Ta to Pt; z = 0, 1-, 2-)

Inorganic Chemistry

Volumn 37, Issue 13, 1998, Pages 3284-3292

  Macgregor, Stuart A ^a,b   Moock, Klaus H ^a  

^a AUSTRALIAN NATIONAL UNIVERSITY   (Australia)

^b HERIOT WATT UNIVERSITY   (United Kingdom)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0001322394     PISSN: 00201669     EISSN: None     Source Type: Journal    
DOI: 10.1021/ic9605736     Document Type: Article

References (62)

1. For part 1, see: Moock, K. H.; Macgregor, S. A.; Heath, G. A.; Derrick S.; Boeré, R. T. J. Chem. Soc., Dalton Trans. 1996, 2067.
2. (a) Moock, K. H.; Rock, M. H. J. Chem. Soc., Dalton Trans. 1993, 2459.
3. (b) Brownstein, S.; Heath, G. A.; Sengupta, A.; Sharp, D. W. A. J. Chem. Soc., Chem. Commun. 1983, 669.
4. (c) Andersen, G. M.; Iqbal, J.; Sharp, D. W. A.; Winfield, J. M.; Cameron, J. H.; McLeod, A. G. J. Fluorine Chem. 1984, 24, 303.
5. (d) Heath, G. A.; Hefter, G. T.; Boyle, T. W.; Desjardins, C. D.; Sharp, D. W. A. J. Fluorine Chem. 1978, 11, 399.
6. (e) Moock, K. H.; Turowsky, L.; Seppelt, K. J. Fluorine Chem. 1987, 37, 253.
7. (f) Sengupta, A. K.; Sharp, D. W. A.; Heath, G. A.; Brownstein, S. J. Fluorine Chem. 1982, 27, 38.
8. Heath, G. A.; Moock, K. H.; Sharp, D. W. A.; Yellowlees, L. J. J. Chem, Soc., Chem. Commun. 1985, 1503.
9. (a) Bartlett, N.; Beaton S. P.; Jha, N. K. J. Chem. Soc., Chem. Commun. 1966, 168.
10. (b) Bartlett, N. Angew. Chem., Int. Ed. Engl 1968, 7, 433.
11. (a) Korobov, M. V.; Kuznetsov, S. V.; Sidorov, L. N.; Shipachev, V. A.; Mit'kin, V. N. Int. J. Mass. Spectrom. Ion Processes 1989, 87, 13.
12. (b) Sidorov, L. N.; Borshchevsky, A. Ya.; Rudny, E. B.; Butsky, V. D. Chem. Phys, 1982, 71, 145,
13. (c) Sidorov, L. N. Usp. Khim. 1982, 51, 625.
14. (d) George, P. M.; Beauchamp, J. L. Chem. Phys. 1979, 36, 345.
15. (e) Burgess, J.; Haigh, I.; Peacock, R. D.; Taylor, P. J. Chem. Soc., Dalton Trans. 1974, 1064.
16. (f) Compton, R. N.; Reinhardt, P. W.; Cooper, C. D. J. Chem. Phys. 1978, 68, 2023.
17. Moock, K. H.; Seppelt, K. Z. Anorg. Allg. Chem. 1988, 561, 132.
18. Bloor, J. E.; Sherrod, R. E. J. Am. Chem. Soc. 1980, 102, 4333.
19. (a) Gutsev, G. L.; Boldyrev, A. I. Chem. Phys. Lett. 1983, 101, 441.
20. (b) Gutsev, G. L.; Boldyrev, A. I. Adv. Chem. Phys. 1985, 61, 169.
21. Gutsev, G. L.; Boldyrev, A. I. J. Phys. Chem. 1990, 94, 2256.
22. Miyoshi, E.; Sakai, Y.; Murakami, A.; Iwaki, H.; Terashima, H.; Shoda, T.; Kawaguchi, T. J. Chem. Phys. 1988, 59, 4193.
23. Cotton, F. A.; Harris, C. B. Inorg. Chem, 1967, 6, 376.
24. Neuhaus, A.; Veldkamp, A.; Frenking, G. Inorg. Chem. 1994, 33, 5278.
25. (a) Rak, J.; Gutowski, M.; Dokurno, P.; Vu Thanh, H.; Blazejowski, J. J. Chem. Phys. 1994, 100, 5810.
26. (b) Gutowski, M.; Boldyrev, A. I.; Ortiz, J. V.; Simons, J. J. Am. Chem. Soc. 1994, 116, 9262.
27. (c) Gutowski, M.; Boldyrev, A. I.; Simons, J. Rak, J.; Blazejowski, J. J. Am. Chem. Soc. 1996, 118, 1173.
28. Deeth, R. J.; Jenkins, H. D. B. J. Phys. Chem. A. 1997, 101, 4793.
29. Winfield, J. M. J. Fluorine Chem. 1984, 25, 91.
30. van Bronswyk, W.; Clark, R. J. H.; Maresca, L. Inorg. Chem. 1969, 8, 1395.
31. Brisdon, B. J.; Fowles, G. W. A.; Tidmarsh, D. J.; Walton, R. A. Spectrochim. Acta 1969, A25, 999.
32. Dickenson, R. N.; Feil, S. E.; Collier, F. N.; Horner, W. W.; Homer, S. M.; Tyree, S. Y. Inorg. Chem. 1964, 3, 1600.
33. Tisley, D. G.; Walton, R. A. J. Chem. Soc. (A) 1971, 3409.
34. Hepworth, M. A.; Robinson P. L.; Westland, G. J. J. Chem. Soc. 1954, 4269.
35. Hepworth, M. A.; Robinson P. L.; Westland, G. J. J. Chem. Soc. 1958, 611.
36. (a) Baerends, E. J.; Ellis, D. E.; Ros, P. Chem. Phys. 1973, 2, 41.
37. (b) Baerends, E. J. In Chemistry and Solid State Physics; Dahl, J. P., Avery, J., Eds., Plenum: New York, 1984.
38. te Velde, G.; Baerends, E. J. J. Comput. Phys. 1992, 99, 84.
39. (a) Snijders, G. J.; Baerends, E. J.; Vernooijs, P. At. Data Nucl. Data Tables 1982, 26, 483.
40. (b) Vernooijs, P.; Snijders, G. J.; Barends, E. J. Slater Type Basis Functions for the hole Periodic System; Internal Report; Free University of Amsterdam: Amsterdam, The Netherlands, 1981.
41. Krijn, J.; Baerends, E. J. Fit Functions in the HFS-method; Internal Report; Free University of Amsterdam: Amsterdam, The Netherlands. 1984.
42. (a) Gunnarsson, O.; Lundqvist, B. I.; Wilkins, J. W. Phys. Rev. B 1974, 10, 1319.
43. (b) Gunnarsson, O.; Lundqvist, B. I. Phys. Rev. B 1976, 13, 4274.
44. (c) Gunnarsson, O.; Jonson, M.; Lundqvist, B. I. Phys. Rev. B 1979, 20, 3136.
45. Vosko, S. H.; Wilk, L.; Nusair, M. Can. J. Phys. 1980, 58, 1200.
46. Versluis, L.; Ziegler, T. J. Chem. Phys. 1988, 88, 322.
47. (a) Ziegler, T.; Tschinke, V.; Baerends, E. J.; Snijders, J. G.; Ravenek, W. J. Phys. Chem. 1989, 93, 3050.
48. (b) van Leeuwen, R.; van Lenthe, E.; Snijders, J. G.; Baerends, E. J. J. Chem. Phys. 1994, 101, 1272.
49. Becke, A. D. J. Chem. Phys. 1986, 84, 4524.
50. Perdew, J. P. Phys. Rev. B 1986, 33, 8822.
51. Bickelhaupt, F. M.; Nibbering, N. M. M.; van Wezenbeck, E. M.; Baerends, E. J. J. Phys. Chem. 1992, 96, 4864.
52. Gillespie, R. J. J. Chem. Educ. 1970, 47, 18.
53. Schäffer C. E.; Jørgensen C. K. J. Inorg. Nucl. Chem. 1958, 8, 143.
54. 0β electron configuration.
55. Macgregor, S. A.; Moock, K. H., work in progress.
56. Kimura, M.; Schomaker, V.; Smith, D. W.; Weinstock, B. J. Chem. Phys. 1968, 48, 4001.
57. Burgess, J.; Fraser, C. J. W.; Haigh, I.; Peacock, R. D. J. Chem. Soc., Dalton Trans. 1973, 501 and references therein.
58. Weinstock, B.; Malm, J. G.; Weaver, E. E. J. Am. Chem. Soc. 1961, 83, 4310.
59. Gmelin Handb. Au Suppl., 1992, B1, pp 158-159.
60. Miyoshi, E.; Sakai, Y. J. Chem. Phys. 1988, 59, 7363.
61. Magnuson R. H. Inorg. Chem. 1984, 23, 387.
62. 2g orbitals are 36.3% and 23.3%, respectively, although the neutral hexafluoride now has the greater electron affinity. Relatively small changes in percentage metal character, therefore, lead to dramatic shifts in the relative electron acceptor abilities of these hexahalometalates, and it is difficult to provide a quantitative rationalization of this on the basis of the percentage metal characters of the acceptor orbitals involved.