Disproportionation and structural changes of tetraarylethylene donors upon successive oxidation to cation radicals and to dications

Journal of the American Chemical Society

Volumn 120, Issue 28, 1998, Pages 6931-6939

  Rathore, R ^a   Lindeman, S V ^a   Kumar, A S ^a   Kochi, J K ^a  

^a University of Houston   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ETHYLENE; OXYGEN RADICAL;

ARTICLE; ELECTRON TRANSPORT; OXIDATION; REACTION ANALYSIS; STRUCTURE ANALYSIS; X RAY DIFFRACTION;

EID: 0032558126     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja981095w     Document Type: Article

References (84)

1. (a) Leigh, W. J.; Arnold, D. R. Can. J. Chem. 1981, 59, 3061.
2. (b) Buckles, R. E.; Hausman, E. A.; Wheeler, N. G. J. Am. Chem. Soc. 1950, 72, 2494.
3. (c) Burchill, P. J. M.; Thorne, N. J. Chem. Soc. C 1968, 696.
4. (d) Bosch, E.; Kochi, J. K. J. Am. Chem. Soc. 1996, 118, 1319.
5. (a) Garst, J. F.; Zablotny, E. R.; Cole, R. S. J. Am. Chem. Soc. 1964, 86, 2257.
6. (b) Schultz, D. A.; Fox M. A. J. Org. Chem. 1990, 55, 1047.
7. (c) Parker, V. D.; Nyberg, K.; Eberson, L. J. Electroanal. Chem. 1969, 22, 150.
8. (a) Buckles, R. E.; Erickson, R. E.; Snyder, J. D.; Person. W. B. J. Am. Chem. Soc. 1960, 82, 2444.
9. (b) Buck, H. M.; Lupinski, J. H.; Oosterhoff, L. I. Mol. Phys. 1958, 1, 196.
10. (c) Buckles, R. E.; Womer, W. D. J. Am. Chem. Soc. 1958, 80, 5055.
11. (d) Bock, H.; Näther, C.; Havlas, Z. J. Chem. Soc., Chem. Commun. 1995, 1111.
12. (a) Buck, H. M.; Bloemhoff, W.; Oosterhoff, L. J. Tetrahedron Lett. 1960, 5.
13. (b) Valenzuela, J. A.; Bard, A. J. J. Phys. Chem. 1968, 72, 286.
14. Bard, A. J. Pure Appl. Chem. 1971, 25, 379.
15. (a) Grzeszczuk, M.; Smith, D. E. J. Electroanal. Chem. 1984, 162, 189.
16. (b) Troll, T.; Baizer, M. M. Electrochim. Acta 1974, 19, 951.
17. (c) Wolf, M. O.; Fox, H. H.; Fox, M. A. J. Org. Chem. 1996, 61, 287.
18. For a recent discussion of the mechanistic ambiguity, see: Rathore, R.; Kochi, J. K. Acta Chem. Scand. 1998, 52, 114.
19. (a) E°1 and E°2 refer to the reversible one-electron oxidation (or reduction) of tetraarylethylene and its cation radical (or anion radical), respectively.
20. (b) When ΔG is expressed in electron volts, the Faraday constant F is unity.
21. (c) Any ion-pairing effects are ignored.
22. (d) For anion radicals, compare: Muzyka, J. L.; Fox, M. A. J. Org. Chem. 1991, 56, 4549. Fry, A. J.; Hutchins, C. S.; Chung, L. L. J. Am. Chem. Soc. 1975, 97, 591. See also Garst et al. in ref 2a.
23. (d) For anion radicals, compare: Muzyka, J. L.; Fox, M. A. J. Org. Chem. 1991, 56, 4549. Fry, A. J.; Hutchins, C. S.; Chung, L. L. J. Am. Chem. Soc. 1975, 97, 591. See also Garst et al. in ref 2a.
24. (a) Mislow, K.; Schultz, D. A.; Fox, M. A. J. Org. Chem. 1990, 55, 1047.
25. (b) Baenziger, N. C.; Buckles, R. E.; Simpson, T. D. J. Am. Chem. Soc. 1967, 89, 3406. See also Buck et al. in ref 4a.
26. There are no reports extant in which the cation-radical and dication structures of the same donor are available for direct comparison.
27. (a) Phelps, J.; Bard, A. J. J. Electroanal. Chem. 1976, 68, 313.
28. (b) Aalstad, B.; Parker, V. D. J. Electroanal. Chem. 1982, 136, 251.
29. Svanholm, U.; Jensen, B. S.; Parker, V. D. J. Chem. Soc., Perkin Trans. 2 1974, 907.
30. 14
31. Rathore, R.; Kochi, J. K. J. Org. Chem. 1995, 60, 4399.
32. Compare Buck et al. in ref 4a.
33. 2] was prepared at - 78 °C and handled without allowing the temperature to rise (see Experimental Section).
34. 2+ was not kinetically persistent (probably due to the presence of labile α-protons on the ethyl groups).
35. Bard, A. J.; Ledwith, A.; Shine, H. J. Adv. Phys. Org. Chem. 1976, 13, 155.
36. For the stoichiometry of the donor oxidation with antimony(V) oxidants, see: Rathore, R.; Kumar, A. S.; Lindeman, S. V.; Kochi, J. K. Submitted for publication.
37. See Experimental Section in Supporting Information Available for details.
38. -] described in the Supporting Information Available.
39. +• from the dark purple solution.
40. 5 was not an effective oxidant of tetraanisylethylene (as in the conproportionation exchange in eq 8).
41. Komatsu, K.; Nishinaga, T.; Aonuma, S.; Hirosawa, C.; Takeuchi, K.; Lindner, H. J.; Richter, J. Tetrahedron Lett. 1991, 32, 6767. For an efficient alternative synthesis of 8, see: Rathore, R.; Lindeman, S. V.; Kumar, A. S.; Kochi, J. K. J. Am. Chem. Soc., in press.
42. Komatsu, K.; Nishinaga, T.; Aonuma, S.; Hirosawa, C.; Takeuchi, K.; Lindner, H. J.; Richter, J. Tetrahedron Lett. 1991, 32, 6767. For an efficient alternative synthesis of 8, see: Rathore, R.; Lindeman, S. V.; Kumar, A. S.; Kochi, J. K. J. Am. Chem. Soc., in press.
43. See: Nishinaga, T.; Komatsu, K.; Sugita, N. J. Am. Chem. Soc. 1993, 115, 11642.
44. The peculiar CV behavior of tetraanisylethylene in nitromethane is subject to further study.
45. As indicated by the separation Δ ∼ 120 mV that is the same as that in tetraanisylethylene.
46. 23
47. 11a by digital simulation of the cyclic voltammetric data.
48. Osteryoung, J. G.; Osteryoung, R. A. Anal. Chem. 1985, 57, 101 A.
49. 2 (vide infra).
50. 2′). (33) The structural parameters l, φ, and q for D = tetraanisylethylene in Chart 3 are plotted as values averaged over all four anisyl groups.
51. ox = 0.43 and 0.37 V vs SCE in dichloromethane and acetonitrile, respectively.
52. (a) Where Ad = 1-adamantyl.
53. + is substituted with a 3-chloro substituent.
54. 2 = 63.7°.
55. Note that 1,1-dianisyl substitution as in 6 is not sufficient to stabilize the dication (Table 3, entry 6).
56. 2 = 1.377 Å, φ = 36.5 deg, q = 39%.
57. (a) Bock, H.; Ruppert, K.; Merzweiler, K.; Fenske, D.; Goesmann, H. Angew. Chem., Int. Ed., Engl. 1989, 20, 1684.
58. (b) Elbl-Weiser, K.; Krieger, C.; Staab, H. A. Angew. Chem., Int. Ed. Engl. 1990, 29, 211.
59. (c) Takanori, S.; Shiohara, H.; Monobe, M.; Sakimura, T.; Tanaka, S.; Yamashita, Y.; Miyashi, T. Angew. Chem., Int. Ed. Engl. 1992, 31, 455.
60. (d) Bock, H.; Näther, C.; Havlas, Z. J. Chem. Soc., Chem. Commun. 1995, 1111. See also:
61. (e) Baenziger, N. C.; Buckles, R. E.; Simpson. T. D. J. Am. Chem. Soc. 1967, 89, 3405.
62. (a) Lammertsma, K.; Barzaghi, M.; Olah, G. A.; Pople, J. A.; Kos, A. J.; Schleyer, P. v. R. J. Am. Chem. Soc. 1983, 105, 5252.
63. (b) Lammertsma, K.; Schleyer, P. v. R.; Schwarz, H. Angew. Chem., Int. Ed. Engl. 1989, 28, 1321 and references therein.
64. Merer, A. J.; Schoonveld, L. Can. J. Phys. 1969, 47, 1731. Koppel, H.; Domcke, W.; Cederbaum, L. S.; von Niessen, W. J. Chem. Phys. 1978, 69, 4252. See also: Shiotani, M.; Nagata, Y.; Sohma, J. J. Am. Chem. Soc. 1984, 106, 4604. Fujisawa, J.; Sato, S.; Shimokoshi, K. Chem. Phys. Lett. 1986, 124, 391.
65. Merer, A. J.; Schoonveld, L. Can. J. Phys. 1969, 47, 1731. Koppel, H.; Domcke, W.; Cederbaum, L. S.; von Niessen, W. J. Chem. Phys. 1978, 69, 4252. See also: Shiotani, M.; Nagata, Y.; Sohma, J. J. Am. Chem. Soc. 1984, 106, 4604. Fujisawa, J.; Sato, S.; Shimokoshi, K. Chem. Phys. Lett. 1986, 124, 391.
66. Merer, A. J.; Schoonveld, L. Can. J. Phys. 1969, 47, 1731. Koppel, H.; Domcke, W.; Cederbaum, L. S.; von Niessen, W. J. Chem. Phys. 1978, 69, 4252. See also: Shiotani, M.; Nagata, Y.; Sohma, J. J. Am. Chem. Soc. 1984, 106, 4604. Fujisawa, J.; Sato, S.; Shimokoshi, K. Chem. Phys. Lett. 1986, 124, 391.
67. Merer, A. J.; Schoonveld, L. Can. J. Phys. 1969, 47, 1731. Koppel, H.; Domcke, W.; Cederbaum, L. S.; von Niessen, W. J. Chem. Phys. 1978, 69, 4252. See also: Shiotani, M.; Nagata, Y.; Sohma, J. J. Am. Chem. Soc. 1984, 106, 4604. Fujisawa, J.; Sato, S.; Shimokoshi, K. Chem. Phys. Lett. 1986, 124, 391.
68. (a) Lunell, S.; Eriksson, L. A.; Huang, M. B. J. Mol. Struct. (THEOCHEM) 1991, 230, 263.
69. (b) Dewar, M. J. S.; Thiel, W. J. Am. Chem. Soc. 1977, 99, 4899.
70. (c) Bellville, D. J.; Bauld, N. L. J. Am. Chem. Soc. 1982, 104, 294.
71. (d) Alvarez-Idaboy, J. R.; Eriksson, L. A.; Fängström, T.; Lunell, S. J. Phys. Chem. 1993, 97, 12737. For twisting in other cation radicals see:
72. (e) Clark, T.; Nelsen, S. F. J. Am. Chem. Soc. 1988, 110, 868.
73. (f) Takahashi, O.; Kikuchi, O. J. Mol. Struct. (Theochem.) 1994, 313, 207.
74. (g) Gerson, F.; Lopez, J.; Krebs, A.; Wolfgang, R. Angew. Chem., Int. Ed. Engl. 1981, 20, 95.
75. (a) Bock, H.; Ruppert, K.; Fenske, D. Angew. Chem., Int. Ed. Engl. 1989, 28, 1685. Compare also:
76. (b) Walczack, M.; Stucky, G. D. J. Organomet. Chem. 1975, 97, 313. Sekiguchi, A.; Nakanishi, T.; Kabuto, C.; Sakurai, H. J. Am. Chem. Soc. 1989, 111, 3748. For the progressive structural changes in tetracyanoethylene, anion radical, and dianion with various countercations, see: Bock, H.; Ruppert, K.; Näther, C.; Havlas, Z.; Hermann, H.-F.; Arad, C.; Göbal, I.; John, A.; Meuret, J.; Nick, S.; Rauschenbach, A.; Seitz, W.; Vaupel, T.; Solokui, B. Angew. Chem., Int. Ed. Engl. 1992, 31, 550 and references therein. Note also that theoretical calculations on ethylene dianion predict θ = 90° and d = 1.40 Å. Kos, A. J.; Jemmis, E. D.; Schleyer, P. v. R.; Gleiter, R.; Fishback, V.; Pople, J. A. J. Am. Chem. Soc. 1981, 103, 4996.
77. (b) Walczack, M.; Stucky, G. D. J. Organomet. Chem. 1975, 97, 313. Sekiguchi, A.; Nakanishi, T.; Kabuto, C.; Sakurai, H. J. Am. Chem. Soc. 1989, 111, 3748. For the progressive structural changes in tetracyanoethylene, anion radical, and dianion with various countercations, see: Bock, H.; Ruppert, K.; Näther, C.; Havlas, Z.; Hermann, H.-F.; Arad, C.; Göbal, I.; John, A.; Meuret, J.; Nick, S.; Rauschenbach, A.; Seitz, W.; Vaupel, T.; Solokui, B. Angew. Chem., Int. Ed. Engl. 1992, 31, 550 and references therein. Note also that theoretical calculations on ethylene dianion predict θ = 90° and d = 1.40 Å. Kos, A. J.; Jemmis, E. D.; Schleyer, P. v. R.; Gleiter, R.; Fishback, V.; Pople, J. A. J. Am. Chem. Soc. 1981, 103, 4996.
78. (b) Walczack, M.; Stucky, G. D. J. Organomet. Chem. 1975, 97, 313. Sekiguchi, A.; Nakanishi, T.; Kabuto, C.; Sakurai, H. J. Am. Chem. Soc. 1989, 111, 3748. For the progressive structural changes in tetracyanoethylene, anion radical, and dianion with various countercations, see: Bock, H.; Ruppert, K.; Näther, C.; Havlas, Z.; Hermann, H.-F.; Arad, C.; Göbal, I.; John, A.; Meuret, J.; Nick, S.; Rauschenbach, A.; Seitz, W.; Vaupel, T.; Solokui, B. Angew. Chem., Int. Ed. Engl. 1992, 31, 550 and references therein. Note also that theoretical calculations on ethylene dianion predict θ = 90° and d = 1.40 Å. Kos, A. J.; Jemmis, E. D.; Schleyer, P. v. R.; Gleiter, R.; Fishback, V.; Pople, J. A. J. Am. Chem. Soc. 1981, 103, 4996.
79. (b) Walczack, M.; Stucky, G. D. J. Organomet. Chem. 1975, 97, 313. Sekiguchi, A.; Nakanishi, T.; Kabuto, C.; Sakurai, H. J. Am. Chem. Soc. 1989, 111, 3748. For the progressive structural changes in tetracyanoethylene, anion radical, and dianion with various countercations, see: Bock, H.; Ruppert, K.; Näther, C.; Havlas, Z.; Hermann, H.-F.; Arad, C.; Göbal, I.; John, A.; Meuret, J.; Nick, S.; Rauschenbach, A.; Seitz, W.; Vaupel, T.; Solokui, B. Angew. Chem., Int. Ed. Engl. 1992, 31, 550 and references therein. Note also that theoretical calculations on ethylene dianion predict θ = 90° and d = 1.40 Å. Kos, A. J.; Jemmis, E. D.; Schleyer, P. v. R.; Gleiter, R.; Fishback, V.; Pople, J. A. J. Am. Chem. Soc. 1981, 103, 4996.
80. 44 The observed deviations in the values of θ from 90° in various tetraarylethylene dications may be a result of crystal packing forces.
81. See, e.g.: Oki, M. Top. Stereochem. 1983, 14, 1.
82. McMurry, J. E.; Fleming, M. P. J. Am. Chem. Soc. 1974, 96, 4708.
83. Rathore, R.; Weigand, U.; Kochi, J. K. J. Org. Chem. 1996, 61, 5246.
84. Hart, H.; Teuerstein, A.; Babin, M. A. J. Am. Chem. Soc. 1981, 103, 903.