The cyclooctatriene-η2-ynyl potassium zwitterionic radical: Evidence for a potassium organometallic

Journal of the American Chemical Society

Volumn 125, Issue 37, 2003, Pages 11212-11213

  Peters, Steven J ^a   Turk, Matthew R ^a   Kiesewetter, Matthew K ^a   Reiter, Richard C ^a   Stevenson, Cheryl D ^a  

^a ILLINOIS STATE UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKALI METAL; ALKYNE; AMPHOLYTE; ANION; POTASSIUM; RADICAL; TETRAHYDROFURAN;

ARTICLE; ELECTRON SPIN RESONANCE;

EID: 0042192054     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja0371698     Document Type: Article

References (19)

1. Szwarc, M. In Ions and Ion Pairs in Organic Reactions: Szwarc, M., Ed.; John Wiley and Sons: New York, 1974; Vol. 2.
2. (a) Hirota J. Phys. Chem. 1967, 71, 127.
3. (b) Strauss, H. L.; Katz, T. J.; Fraenkel, G. K. J. Am. Chem. Soc. 1963, 85, 2360.
4. (a) Jones, M. T.; Kuechler T. C. J. Phys. Chem. 1977, 81, 360.
5. (b) Williams, W. G.; Pritchett, R. J.; Fraenkel, G. K. J. Chem. Phys. 1970, 52, 5584.
6. (a) Stevenson, C. D.; Colon, M.; Concepcion, J. G.; Block, A. J. Am. Chem. Soc. 1974, 96, 2283.
7. (b) The original conditions (ref 4a) were modified (the addition of potassium tert-butoxide) to obtain much better yields of the alkyne.
8. (c) Stevenson, C. D.; Wagner, E. P.; Reiter, R. C. J. Phys. Chem. 1993, 97, 10585.
9. At 150 K. potassium splittings from ion pairs are always too small to observe.
10. Stevenson, C. D.; Wagner, E. P.; Reiter, R. C. Inorg. Chem. 1993, 32, 2480.
11. (a) Eastman, M. P.; Ramirez, D. A.; Jager, C. D.; Watts, M. T. J. Phys. Chem. 1976, 80, 182.
12. (b) Watts, M. T.; Lu, M. L.; Chen, R. C.; Eastman, M. P. J. Phys. Chem. 1973, 77, 2959.
13. (c) Gokel, G. Crown Ethers & Cryptands; The Royal Society of Chemistry: Cambridge, England, 1991.
14. Huheey, J. E.; Keiter, E. A.; Keiter, R. L. Inorganic Chemistry: Principles of Structure and Reactivity, 4th ed.; HarperCollins: New York, 1993.
15. The total spectral width is 26.5 G (see ref 2b), and the modern theoretical interpretation of it appears in: Hammons, J. H.; Hrovat, D. A.; Borden, W. T. J. Am. Chem. Soc. 1991, 113, 4500.
16. (a) Weil, J. A.; Bolton, J. R.; Wertz, J. E. Electron Paramagnetic Resonance; John Wiley and Sons: New York, 1994; p 241.
17. (b) Applied to cyclooctatetraenyl systems in: Stevenson, C. D.; Kim, Y. S. J. Am. Chem. Soc. 2000, 122, 3211.
18. When the reduction is carried out with lithium metal, an analogous result is obtained, and no hyperfine splitting from the Li counterion is observed.
19. The thermal instability of the anion radical coupled with the fact that we are near the freezing point of the solvent prevents the acquisition of enthalpic data.