Multiple-electron transfer in a single step. Design and synthesis of highly charged cation-radical salts

Organic Letters

Volumn 3, Issue 18, 2001, Pages 2887-2890

  Rathore, Rajendra ^a   Burns, Carrie L ^a   Deselnicu, Mihaela I ^a  

^a Marquette University   (United States)

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ARTICLE;

EID: 0001127169     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol0163474     Document Type: Article

References (41)

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22. 2 (70 mg, 0.1 mmol), under a flow of argon. The resulting pale yellow reaction mixture was refluxed for 12 h and cooled to room temperature. A standard aqueous workup and recrystallization of the crude solid from a dichloromethane/ethanol mixture afforded pure 1c in 96% yield. Compare: Kumada, K. Pure Appl. Chem. 1980, 52, 669.
23. 8: C, 79.54; H, 6.57; O, 13.90. Found: C, 79.44; H, 6.48. These structures were further confirmed by high-resolution mass spectra.
24. 2: C, 79.31; H, 7.49; O, 13.21. Found: C, 79.22; H, 7.58.
25. The reduced current response for equimolar 1c (or 2c) as compared to the ferrocene as an added internal standard can be readily attributed to the difference in the diffusion coefficient of 1c (or 2c) due to difference in the size and the shape; see: Flanagan, J. B.; Margel, S.; Bard, A. J.; Anson, F. C. J. Am. Chem. Soc. 1978, 100, 4248. However, a preliminary cyclic voltammetric study, which will be published elsewhere, showed a current ratio of 1 with an equimolar solution of 1c and hexakis(4-ferrocenylphenyl)-benzene as an internal standard: Rathore, R.; Burns, C. L., unpublished results.
26. 5, see: Rathore, R.; Kumar, A. S.; Lindeman, S. V.; Kochi, J. K. J. Org. Chem. 1998, 63, 5847.
27. -)4] was determined by iodometric titration and was found to be greater than 98%. For a general procedure for iodometric titrations of cation radicals, see: Rathore, R.; Kochi, J. K. J. Org. Chem. 1995, 60, 4399 and also ref 9.
28. Rathore, R.; Le Maguères, P.; Lindeman, S. V.; Kochi, J. K. Angew. Chem., Int. Ed. 2000, 39, 809. Also see: Rathore, R.; Le Maguères, P.; Kochi, J. K. J. Org. Chem. 2000, 65, 6826.
29. Rathore, R.; Le Maguères, P.; Lindeman, S. V.; Kochi, J. K. Angew. Chem., Int. Ed. 2000, 39, 809. Also see: Rathore, R.; Le Maguères, P.; Kochi, J. K. J. Org. Chem. 2000, 65, 6826.
30. 6 at 0°C.
31. -1.
32. The lack of electronic communication amongst various aryl groups in 1c can be attributed to the propeller shape of the hexaphenylbenzene framework. We believe that the synthesis of an analogue of 1c (in progress) in which the six aryl groups are connected to planar hexa-peri-hexabenzocoronene framework will lead to extensive electronic communication amongst aryl groups. Compare: Ito, S.; Herwig, P. T.; Böhme, T.; Rabe, J. P.; Rettig, W.; Müllen, K. J. Am. Chem. Soc. 2000, 122, 7698.
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39. Rathore, R.; Le Maguères, P.; Kochi, J. K. J. Org. Chem. 2000, 65, 6826.
40. Cation radicals of various donors mentioned here have been characterized previously; see: (a) Rathore, R.; Lindeman, S. V.; Kumar, A. S.; Kochi, J. K. J. Am. Chem. Soc. 1998, 120, 6931.
41. (b) Rathore, R.; Kumar, A. S.; Lindeman, S. V.; Kochi, J. K. J. Org. Chem. 1998, 63, 5847 and references therein.