Relation of structural changes to electron-transfer parameters in fulvalenediyl dirhodium complexes demonstrating quasi-reversible two-electron voltammetry

Journal of the American Chemical Society

Volumn 118, Issue 21, 1996, Pages 5002-5010

  Chin, Teen T ^a   Geiger, William E ^a   Rheingold, Arnold L ^a  

^a UNIVERSITY OF VERMONT   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CHARACTERIZATION; CHARGE TRANSFER; CYCLIC VOLTAMMETRY; ELECTROLYTIC ANALYSIS; INFRARED SPECTROSCOPY; ORGANOMETALLICS; OXIDATION; REACTION KINETICS;

BOND DISTANCES; COULOMETRY; FULVALENEDIYL DIRHODIUM COMPLEXES; ROTATION BARRIERS;

RHODIUM COMPOUNDS;

RHODIUM DERIVATIVE;

ARTICLE; COULOMETRY; ELECTRON TRANSPORT; INFRARED SPECTROSCOPY; OXIDATION; POTENTIOMETRY; X RAY CRYSTALLOGRAPHY;

EID: 15844385775     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja960259a     Document Type: Article

References (58)

1. - (cyclopentadienyl) ligand.
2. pc, et = electron transfer, Fv = fulvalenediyl, OTTLE = optically transparent thin layer electrode, v = scan rate.
3. Geiger, W. E.; Salzer, A.; Edwin, J.; von Philipsborn, W.; Piantini, U.; Rheingold, A. L. J. Am. Chem. Soc. 1990, 112, 7113.
4. Rhodes, M. R.; Mann, K. R. Inorg. Chem. 1984, 23, 2053.
5. Smith, D. A.; Zhuang, B.; Newton, W. E.; McDonald, J. W.; Schultz, F. A. Inorg. Chem. 1987, 26, 2524.
6. Koide, Y.; Bautista, M. T.; White, P. S.; Schauer, C. K. Inorg. Chem. 1992, 31, 3690.
7. Collman, J. P.; Rothrock, R. K.; Finke, R. G.; Moore, E. J.; Rose-Munch, F. Inorg. Chem. 1982, 21, 146.
8. Connelly, N. G.; Lucy, A. R.; Payne, J. D.; Galas, A. M. R.; Geiger, W. E. J. Chem. Soc., Dalton Trans. 1983, 1879.
9. Fernandes, J. B.; Zhang, L. Q.; Schultz, F. A. J. Electroanal. Chem. 1991, 297, 145.
10. Lockemeyer, J. R.; Rauchfuss, T. B.; Rheingold, A. L. J. Am. Chem. Soc. 1989, 111, 5733.
11. Finke, R. G.; Voegeli, R. H.; Laganis, E. D.; Boekelheide, V. Organometallics, 1983, 2, 347.
12. (a) Bowyer, W. J.; Merkert, J. W.; Geiger, W. E. Organometallics 1989, 8, 191.
13. (b) Bowyer, W. J.; Geiger, W. E. J. Electroanal. Chem. 1988, 239, 253.
14. Thompson, R. L.; Geib, S. J.; Cooper, N. J. J. Am. Chem. Soc. 1991, 113, 8961.
15. Rieke, R. D.; Arney, J. S.; Rich, W. E.; Willeford, B. R., Jr.; Poliner, B. S. J. Am. Chem. Soc. 1975, 97, 5951.
16. Pierce, D. T.; Geiger, W. E. J. Am. Chem. Soc. 1992, 114, 6063.
17. For leads to CEE, ECE, and EEC processes, see refs 28-43 of ref 15.
18. Pugh, J. R.; Meyer, T. J. J. Am. Chem. Soc. 1992, 114, 3784.
19. (a) Saveant, J. M. In Advances in Electron Transfer Chemistry; Mariano, P. S., Ed.; JAI Press: New York, 1994; Vol. 4, p 53.
20. (b) Andrieux, C. P.; Robert, M.; Saveant, J.-M. J. Am. Chem. Soc. 1995, 117, 9340 and references therein.
21. Moulton, R.; Weidman, T. W.; Vollhardt, K. P. C.; Bard, A. J. Inorg. Chem. 1986, 25, 1846.
22. Brown, D.; Delville-Desbois, M. H.; Vollhardt, K. P. C.; Astruc, D. New J. Chem. 1992, 16, 899.
23. Bitterwolf, T. E.; Spink, W. C.; Rausch, M. D. J. Organomet. Chem. 1989, 363, 189.
24. Vollhardt, K. P. C.; Weidman, T. W. Organometallics 1984, 3, 82 and references therein.
25. One fulvalenediyl complex with two 17-electron metals which most likely has an anti orientation is the biferrocenium dication: (a) Morrison, W. H., Jr.; Hendrickson, D. N. J. Chem. Phys. 1973, 59, 380.
26. (b) Levanda, C.; Bechgaard, K.; Cowan, D. O. J. Org. Chem. 1976, 41, 2700. For a summary of redox chemistry in fulvalenediyl complexes, see; Astruc, D. Electron Transfer and Radical Processes in Transition-Metal Chemistry; VCH Publishers: New York, 1995; pp 154-60.
27. (b) Levanda, C.; Bechgaard, K.; Cowan, D. O. J. Org. Chem. 1976, 41, 2700. For a summary of redox chemistry in fulvalenediyl complexes, see; Astruc, D. Electron Transfer and Radical Processes in Transition-Metal Chemistry; VCH Publishers: New York, 1995; pp 154-60.
28. Freeman, M. J.; Orpen, A. G.; Connelly, N. G.; Manners, I.; Raven, S. J. J. Chem. Soc., Dalton Trans. 1985, 2283.
29. Rausch, M. D.; Spink, W. C. J. Organomet. Chem. 1986, 308, C1.
30. Feldberg, S. W. In Electroanalytical Chemistry; Bard, A. J., Ed.; Marcel Dekker: New York, 1969; Vol. 3, p 199. Copies of these programs (in Fortran) may be obtained from the corresponding author.
31. Atwood, C. G.; Geiger, W. E.; Bitterwolf, T. E. J. Electroanal. Chem. 1995, 397, 279.
32. 29 for a soluble electrode product. This behavior is diagnostic of electrode product film formation at the electrode surface.
33. Schwarz, W. M; Shain, I. J. Phys. Chem. 1965, 69, 30.
34. Nakamoto, K. Infrared and Raman Spectra of Inorganic and Coordination Compounds, 4th ed.; John Wiley: New York, 1986; pp 291-295.
35. Geoffroy, G. L.; Wrighton, M. S. Organometallic Photochemistry; Academic Press: New York, 1979; pp 20-22.
36. (a) Levenson, R. A.; Gray, H. B.; Caesar, G. P. J. Am. Chem. Soc. 1970, 92, 3653.
37. (b) Levenson, R. A.; Gray, H. B. J. Am. Chem. Soc. 1975, 97, 6042.
38. (c) Jackson, R. A.; Poe, A. Inorg. Chem. 1978, 17, 997.
39. -1 in Nujol.
40. Ryan, M. D. J. Electrochem. Soc. 1978, 125, 547.
41. Myers, R. L.; Shain, I. Anal. Chem. 1969, 41, 980.
42. Richardson, D. E.; Taube, H. Inorg. Chem. 1981, 20, 1278.
43. 2+ will be less than twice that of ferrocene/ferrocenium. Values of 1.9 to 1.3 are predicted from the Randles-Sevcik equation depending on whether one or two electrons are transfered in the rate-determining step. The measured value of 1.8 may be taken as evidence for an overall two-electron process, but drawing further conclusions about the n value in the rate-determining et would, in our view, be speculative.
44. -1/2, intercept = 7.1 μC.
45. Edwin, J.; Geiger, W. E. J. Am. Chem. Soc. 1990, 112, 7104.
46. Rongfeng, Z.; Evans, D. H. J. Electroanal. Chem. 1995, 385, 201.
47. Vollhardt, K. P. C.; Weidman, T. W. J. Am. Chem. Soc. 1983, 105 1676.
48. Tommasino, J.-B.; de Montauzon, D.; He, X.; Maisonnat, A.; Poilblanc, R.; Verpeaux, J.-N.; Amatore, C. Organometallics 1992, 11, 4150.
49. Evans, D. H.; O-Connell, K. M. In Electroanalytical Chemistry; Bard, A. J., Ed.; Marcel Dekker: New York, 1986; Vol. 14, p 113.
50. Marcus, R. A. J. Chem. Phys. 1965, 43, 679.
51. Bard, A. J.; Faulkner, L. R. Electrochemical Methods; John Wiley: New York, 1980; p 97.
52. Weaver, M. J.; Gennett, T. Chem. Phys. Lett. 1985, 113, 213.
53. Lichtenberger, D. L.; Gruhn, N. E.; Rempe, M. E.; Geiger, W. E.; Chin, T. T. Inorg. Chim. Acta 1995, 240, 623.
54. (a) Gingerich, K. A.; Gupta, S. K. J. Chem. Phys. 1978, 69, 505.
55. (b) Goursot, A.; Papai, I.; Salahub, D. R. J. Am. Chem. Soc. 1992, 114, 7452.
56. Harvey, P. D.; Shafiq, F.; Eisenberg, R. Inorg. Chem. 1994, 33, 3424.
57. Connor, J. A. In Transition Metal Clusters; Johnson, B. F. G., Ed.; Wiley: Chichester, 1980; p 356 ff.
58. From the Pauling-Badger relation, see: Sims, L. B.; Lewis, D. E. In Isotopes in Organic Chemistry; Buncel, E., Lee, C. C., Eds.; Elsevier: Amsterdam, 1984; Vol. 6, p 184 ff.