Primitive Molecular Recognition Effects in Electron Transfer Processes: Modulation of ((Trimethylammonio)methyl)ferrocenium/ferrocene Self-Exchange Kinetics via Hydrophobic Encapsulation

Inorganic Chemistry

Volumn 35, Issue 4, 1996, Pages 970-973

  Nielson, Roger M ^a,b   Andrew Lyon, L ^a   Hupp, Joseph T ^a  

^a NORTHWESTERN UNIVERSITY   (United States)

^b SOUTHERN OREGON UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000821358     PISSN: 00201669     EISSN: None     Source Type: Journal    
DOI: 10.1021/ic950569e     Document Type: Article

References (34)

1. Representative kinetic studies: (a) Imonigie, J. A.; Macartney, D. H. Inorg. Chem. 1993, 32, 1007. (b) Imonigic, J. A.; Macartney, D. H. J. Chem. Soc., Dalton Trans. 1993, 1830. (c) Imonigie, J. A.; Macartney, D. H. Inorg. Chim. Acta 1994, 225, 51. (d) Johnson, M. D.; Reinsborough, V. C.; Ward, S. Inorg. Chem. 1992, 31, 1085.
2. Representative kinetic studies: (a) Imonigie, J. A.; Macartney, D. H. Inorg. Chem. 1993, 32, 1007. (b) Imonigic, J. A.; Macartney, D. H. J. Chem. Soc., Dalton Trans. 1993, 1830. (c) Imonigie, J. A.; Macartney, D. H. Inorg. Chim. Acta 1994, 225, 51. (d) Johnson, M. D.; Reinsborough, V. C.; Ward, S. Inorg. Chem. 1992, 31, 1085.
3. Representative kinetic studies: (a) Imonigie, J. A.; Macartney, D. H. Inorg. Chem. 1993, 32, 1007. (b) Imonigic, J. A.; Macartney, D. H. J. Chem. Soc., Dalton Trans. 1993, 1830. (c) Imonigie, J. A.; Macartney, D. H. Inorg. Chim. Acta 1994, 225, 51. (d) Johnson, M. D.; Reinsborough, V. C.; Ward, S. Inorg. Chem. 1992, 31, 1085.
4. Representative kinetic studies: (a) Imonigie, J. A.; Macartney, D. H. Inorg. Chem. 1993, 32, 1007. (b) Imonigic, J. A.; Macartney, D. H. J. Chem. Soc., Dalton Trans. 1993, 1830. (c) Imonigie, J. A.; Macartney, D. H. Inorg. Chim. Acta 1994, 225, 51. (d) Johnson, M. D.; Reinsborough, V. C.; Ward, S. Inorg. Chem. 1992, 31, 1085.
5. Representative thermodynamic studies: (a) Zhang, L.; Macias, A.; Lu, T.; Gordon, J. I.; Gokel, G. W.; Kaifer, A. E. J. Chem. Soc., Chem. Commun. 1993, 1017. (b) Isnin, R.; Salam, C.; Kaifer, A. E. J. Org. Chem. 1991, 37, 1939. (c) Strelets, V. V.; Mamedjarov, I. A ; Nefedova, M. N.; Pysnograeva, V. I.; Sokolov, V. I.; Pospisil, L.; Hanzlik, J. J. Electroanal. Chem. 1991, 310, 179. (d) Ando, I.; Ishimura, D.; Ujimoto, K.; Kurihara, H. Inorg. Chem. 1994, 33, 5010.
6. Representative thermodynamic studies: (a) Zhang, L.; Macias, A.; Lu, T.; Gordon, J. I.; Gokel, G. W.; Kaifer, A. E. J. Chem. Soc., Chem. Commun. 1993, 1017. (b) Isnin, R.; Salam, C.; Kaifer, A. E. J. Org. Chem. 1991, 37, 1939. (c) Strelets, V. V.; Mamedjarov, I. A ; Nefedova, M. N.; Pysnograeva, V. I.; Sokolov, V. I.; Pospisil, L.; Hanzlik, J. J. Electroanal. Chem. 1991, 310, 179. (d) Ando, I.; Ishimura, D.; Ujimoto, K.; Kurihara, H. Inorg. Chem. 1994, 33, 5010.
7. Representative thermodynamic studies: (a) Zhang, L.; Macias, A.; Lu, T.; Gordon, J. I.; Gokel, G. W.; Kaifer, A. E. J. Chem. Soc., Chem. Commun. 1993, 1017. (b) Isnin, R.; Salam, C.; Kaifer, A. E. J. Org. Chem. 1991, 37, 1939. (c) Strelets, V. V.; Mamedjarov, I. A ; Nefedova, M. N.; Pysnograeva, V. I.; Sokolov, V. I.; Pospisil, L.; Hanzlik, J. J. Electroanal. Chem. 1991, 310, 179. (d) Ando, I.; Ishimura, D.; Ujimoto, K.; Kurihara, H. Inorg. Chem. 1994, 33, 5010.
8. Representative thermodynamic studies: (a) Zhang, L.; Macias, A.; Lu, T.; Gordon, J. I.; Gokel, G. W.; Kaifer, A. E. J. Chem. Soc., Chem. Commun. 1993, 1017. (b) Isnin, R.; Salam, C.; Kaifer, A. E. J. Org. Chem. 1991, 37, 1939. (c) Strelets, V. V.; Mamedjarov, I. A ; Nefedova, M. N.; Pysnograeva, V. I.; Sokolov, V. I.; Pospisil, L.; Hanzlik, J. J. Electroanal. Chem. 1991, 310, 179. (d) Ando, I.; Ishimura, D.; Ujimoto, K.; Kurihara, H. Inorg. Chem. 1994, 33, 5010.
9. (a) Todd, M. D.; Yoon, D. I.; Hupp, J. T. Inorg. Chem. 1991, 30, 4685
10. (b) Curtis, J. C.; Roberts, J. A.; Blackbourn, R. L.; Dong, Y.; Massum, M.; Johnson, C. S.; Hupp, J. T. Inorg. Chem. 1991, 30, 3856.
11. (c) Todd, M. D.; Dong, Y.; Horney, J.; Yoon, D. I.; Hupp, J. T. Inorg. Chem. 1993, 32, 2001.
12. (d) Nielson, R. M.; Yoon, D. I.; Hupp, J. T. J. Am. Chem. Soc. 1995, 117, 9085.
13. Lindsay, J. K.; Hauser, C. R. J. Org. Chem. 1957, 22, 355.
14. (a) Rosenblum, M., Brown, N.; Papenmeier, J.; Applebaum, M. J. J. Organomet. Chem. 1966, 6, 173.
15. (b) Dong, T. Y.; Kambara, T.; Hendrickson, D. N. J. Am. Chem. Soc. 1986, 25, 4233.
16. (c)Blackbourn, R. L ; Hupp, J. T. Chem. Phys. Lett. 1988, 150, 399.
17. Nielson, R M.: McManis, G. E.; Weaver, M. J. J. Phys. Chem. 1989, 93, 4703.
18. See, for example: Chan, M. S.; Wahl, A. C. J. Phys. Chem. 1978, 82, 2542.
19. +-β-CD (see eq. 4).
20. It is imponant to note that the relevant concentration in eq 4 is the free host concentration, not the total concentration. The concentrations of free host were determined iteratively.
21. 2+.
22. The solubility limit for β-CD was ∼23 mM (achieved by gently heating the host solution followed by spontaneous cooling to room temperature). Assuming that a 15 mV deviation from Nernstian behavior would be detectable at the highest host concentration, eq 1 and the data in Figure 1 yield the indicated upper limit estimate for K '.
23. Matsue, T.; Evans, D. H.; Osa, T.; Kobayashi, N. J. Am. Chem. Soc. 1985, 107, 3411.
24. See also: Bard, A. J.; Faulkner, L. Electrochemical Methods: Fundamentals and Applications; John Wiley and Sons: New York, 1980 p 445.
25. We thank Prof. M. D. Johnson of New Mexico State University for communicating these results to us prior to publication.
26. While eq 7b is written as a net host transfer reaction, presumably it involves sequential unimolecular dissociation and bimolecular association reaction components.
27. β (small), rate data were fit to a logrithmic form of eq 8.
28. -1 (with electrolyte). The disparity between measured and fit values for the former might be due to noncancelling systematic errors associated with the intercomparison of kinetic data collected in both the slow (eq 1) and fast (eq 2) line broadening regimes
29. 2+ concentration. In contrast, the expected sensitivity is observed experimentally at all accessible host concentrations.
30. 4 solutions. Room temperature rate constants in the two electrolyte solutions were identical in the absence of cyclodextrin, but differed by ∼35% in the presence of cyclodextrin (17 mM).
31. β values at lower temperatures, therefore, required extrapolation of In k° vs 1/T plots.
32. 2O), are ΔS*(0) = -10 eu, ΔS*(17) = -7 eu, and ΔS*(β) = -22 eu. With electrolyte the parameters are ΔS*(0) = -10 eu, ΔS*(17) = -6 eu, and ΔS*(β) = -28 eu.
33. op in a previously published correlation of six solvents (Blackboum, R. L.; Hupp, J. T J. Phys. Chem. 1990, 94, 1788).
34. -1.