Improved electrochemistry in low-polarity media using tetrakis(pentafluorophenyl)borate salts as supporting electrolytes

Angewandte Chemie - International Edition

Volumn 39, Issue 1, 2000, Pages 248-250

  LeSuer, Robert J ^a   Geiger, William E ^a  

^a UNIVERSITY OF VERMONT   (United States)

Author keywords

Borates; Cyclic voltammetry; Electrochemistry; Ion pairing; Oxidations

Indexed keywords

ALKYL ETHER; BORATE SODIUM; ELECTROLYTE; FERROCENE DERIVATIVE; FLUORINE DERIVATIVE; PHENYL GROUP; SOLVENT;

ARTICLE; CHEMICAL REACTION; CYCLIC POTENTIOMETRY; DIELECTRIC CONSTANT; ELECTROCHEMISTRY; POLARIZATION; SOLUBILIZATION;

EID: 0034598481     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/(SICI)1521-3773(20000103)39:1<248::AID-ANIE248>3.0.CO;2-3     Document Type: Article

References (35)

1. a) C. D. Baer, C. A. Camaioni-Neto, D. A. Sweigart, A. M. Bond, T. F. Mann, G. A. Tondreau, Coord. Chem. Rev. 1989, 93, 1;
2. b) A. Abbott, Chem. Soc. Rev. 1993, 435;
3. c) A. Fry in Laboratory Techniques in Electroanalytical Chemistry (Eds.: P. T. Kissinger, W. R. Heineman), 2nd ed., Marcel Dekker, New York, 1996, p. 469;
4. d) D. H. Evans, S. A. Lerke in Laboratory Techniques in Electroanalytical Chemistry (Eds.: P. T. Kissinger, W. R. Heineman), 2nd ed., Marcel Dekker, New York, 1996, p. 487;
5. e) R. Cosmo, C. Kautz, K. Meerholz, J. Heinze, K. Müllen, Angew. Chem. 1988, 101, 638; Angew. Chem. Int. Ed. 1988, 28, 604;
6. e) R. Cosmo, C. Kautz, K. Meerholz, J. Heinze, K. Müllen, Angew. Chem. 1988, 101, 638; Angew. Chem. Int. Ed. 1988, 28, 604;
7. f) S. Ching, J. T. McDevitt, S. R. Peck, R. W. Murray, J. Electrochem. Soc. 1991, 138, 2308;
8. g) C. R. Carbrera, A. J. Bard, J. Electroanal. Chem. 1989, 273, 147;
9. h) M. Tsionsky, A. J. Bard, M. V. Mirkin, J. Am. Chem. Soc. 1997, 119, 10785.
10. N. J. Stone, D. A. Sweigart, A. M. Bond, Organometallics 1986, 5, 2553.
11. M. G. Hill, W. M. Lamanna, K. R. Mann, Inorg. Chem. 1991, 30, 4687.
12. A. R. Siedle, B. Hanggi, R. A. Newmark, K. R. Mann, T. Wilson, Macromol. Symp. 1995, 89, 299.
13. W. E. Piers, T. Chivers, Chem. Soc. Rev. 1997, 345.
14. 3CN have been frequently employed to increase the solubility of both the neutral complexes and their cationic products: a) R. Rulkens, A. J. Lough, I. Manners, S. R. Lovelace, C. Grant, W. E. Geiger, J. Am. Chem. Soc. 1996, 118, 12683;
15. b) B. Grossmann, J. Heinze, E. Herdtweck, F. H. Koehler, H. Noeth, H. Schwenk, M. Spiegler, W. Wachter, B. Weber, Angew. Chem. 1997, 109, 384; Angew. Chem. Int. Ed. 1997, 36, 387.
16. b) B. Grossmann, J. Heinze, E. Herdtweck, F. H. Koehler, H. Noeth, H. Schwenk, M. Spiegler, W. Wachter, B. Weber, Angew. Chem. 1997, 109, 384; Angew. Chem. Int. Ed. 1997, 36, 387.
17. A quantitative study of ion-pairing interactions in metallocene (poly)cations is being conducted. The cobaltocenium/cobaltocene couple was used as an internal standard; see a) R. S. Stojanovic, A. M. Bond, Anal. Chem. 1993, 65, 56;
18. 0 was measured as 1.33 V in separate experiments in both electrolytes, enabling the scaling of Figure 1.
19. C. K. Mann, Electroanalytical Chemistry, Vol. 3 (Ed.: A. J. Bard), Marcel Dekker, New York, 1969, p. 101. Electrochemistry in ethers is normally performed using lithium-based supporting electrolytes; for leading references, see Z. Wang, B. Huang, R. Xue, L. Chen, X. Huang, J. Electrochem. Soc. 1998, 145, 3346.
20. C. K. Mann, Electroanalytical Chemistry, Vol. 3 (Ed.: A. J. Bard), Marcel Dekker, New York, 1969, p. 101. Electrochemistry in ethers is normally performed using lithium-based supporting electrolytes; for leading references, see Z. Wang, B. Huang, R. Xue, L. Chen, X. Huang, J. Electrochem. Soc. 1998, 145, 3346.
21. 6], ambient temperature, 2.3 KΩcm.
22. 1/4 was 112 mV at room temperature and 133 mV at 210 K.
23. 1/2: L. Jeftie, G. Manning, J. Electroanal. Chem. 1970, 26, 195; see also M. E. Peover, J. Chem. Soc. 1962, 4540.
24. 1/2: L. Jeftie, G. Manning, J. Electroanal. Chem. 1970, 26, 195; see also M. E. Peover, J. Chem. Soc. 1962, 4540.
25. 1/2: L. Jeftie, G. Manning, J. Electroanal. Chem. 1970, 26, 195; see also M. E. Peover, J. Chem. Soc. 1962, 4540.
26. D. K. Roe in Laboratory Techniques in Electroanalytical Chemistry (Eds.: P. T. Kissinger, W. R. Heineman), 2nd ed., Marcel Dekker, New York, 1996, p. 195.
27. pc for a Nernstian couple displays a minor dependence on the CV switching potential and is predicted to be 61 mV for a system undergoing fast heterogeneous electron transfer kinetics under our recording conditions; see R. S. Nicholson, Anal. Chem. 1966, 38, 1406.
28. T. Gennett, D. F. Milner, M. J. Weaver, J. Phys. Chem. 1985, 89, 2787, and references therein.
29. D. F. Milner, M. J. Weaver, Anal. Chim. Acta 1987, 198, 245.
30. W. E. Geiger in Laboratory Techniques in Electroanalytical Chemistry (Eds.: P. T. Kissinger, W. R. Heineman), 2nd ed., Marcel Dekker, New York, 1996, p. 683.
31. A. C. Michael, R. M. Wightman in Laboratory Techniques in Electroanalytical Chemistry (Eds.: P. T. Kissinger, W. R. Heineman), 2nd ed., Marcel Dekker, New York, 1996, p. 367.
32. a) S. M. Drew, R. M. Wightman, C. A. Amatore, J. Electroanal. Chem. 1991, 317, 117;
33. b) K. B. Oldham, T. J. Cardwell, J. H. Santos, A. M. Bond, J. Electroanal. Chem. 1997, 430, 39;
34. c) D. Pletcher, H. Thompson, J. Chem. Soc. Faraday Trans. 1998, 94, 3445.
35. Note added in proof (December 13, 1999): Voltammograms of titanium complexes have recently been reported in difluorobenzene using 2 MM tetrabutylammonium tetrakis(pentafluorophenyl)borate as the supporting electrolyte: S. Feng, J. Klosin, W. J. Kruper, Jr., M. H. McAdon, D. R. Neithamer, P. N. Kickias, J. T. Patton, D. R. Wilson, Organometallics 1999, 18, 1159.