Stable hydrocarbon diradical, an analogue of trimethylenemethane

Journal of the American Chemical Society

Volumn 127, Issue 25, 2005, Pages 9014-9020

  Rajca, Andrzej ^a   Shiraishi, Kouichi ^a   Vale, Matthew ^a   Han, Hongxian ^a   Rajca, Suchada ^a  

^a UNIVERSITY OF NEBRASKA LINCOLN   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ANNEALING; LIGHT ABSORPTION; MAGNETIC COUPLINGS; PARAMAGNETIC RESONANCE; PERTURBATION TECHNIQUES; SQUIDS;

BUILDING BLOCKS; FERROMAGNETIC COUPLINGS; HETEROATOM PERTURBATION; TRIMETHYLENEMETHANE (TMM);

HYDROCARBONS;

FERROMAGNETIC MATERIAL; HYDROCARBON; LITHIUM; ORGANOMETALLIC COMPOUND; TETRAHYDROFURAN DERIVATIVE; TRIMETHYLENEMETHANE; UNCLASSIFIED DRUG;

ARTICLE; CHEMICAL ANALYSIS; CHEMICAL STRUCTURE; CYCLIC POTENTIOMETRY; ELECTROCHEMISTRY; ELECTRON SPIN RESONANCE; LIGHT ABSORPTION; MAGNETIC FIELD; MAGNETISM; MOLECULAR INTERACTION; OXIDATION REDUCTION REACTION; ROOM TEMPERATURE; SYNTHESIS; ULTRAVIOLET SPECTROSCOPY;

ELECTRON SPIN RESONANCE SPECTROSCOPY; FREE RADICALS; HYDROCARBONS, AROMATIC; MAGNETICS; METHANE; MOLECULAR STRUCTURE; SPECTROPHOTOMETRY, ULTRAVIOLET;

EID: 21244490733     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja052002v     Document Type: Article

References (71)

1. (a) Dowd, P. J. Am. Chem. Soc. 1966, 88, 2587-2589.
2. (b) Dowd, P. Acc. Chem. Res. 1972, 5, 242-248.
3. (c) Baseman, R. J.; Pratt, D. W.; Chow. M.; Dowd, P. J. Am. Chem. Soc. 1976, 98, 5726-5727.
4. (d) Cramer, C. J. J. Chem. Soc., Perkin Trans. 2 1998, 1007-1013.
5. (a) Berson, J. A. In Reactive Intermediate Chemistry; Moss, R. A., Platz, M. S., Jones, M., Jr., Eds.; Wiley: Hoboken, NJ, 2004; Chapter 5, pp 165-203.
6. (b) Berson, J. A. Acc. Chem. Res. 1978, 11, 446-453.
7. (c) Platz, M. S.; McBride, J. M.; Little, R. D.; Harrison, J. J.; Shaw, A.; Potter, S. E.; Berson, J. A. J. Am. Chem. Soc. 1976, 98, 5725-5726.
8. (a) Borden, W. T.; Davidson, E. R. J. Am. Chem. Soc. 1977, 99, 4587-4594.
9. (b) Borden, W. T. In Diradicals; Borden, W. T., Ed.; Wiley: New York. 1982; Chapter 1.
10. (a) Ma, B.; Schaefer, H. F. Chem. Phys. 1996, 207, 31-41.
11. (b) Cramer, C. J.; Smith, B. A. J. Phys. Chem. 1996, 100, 9664-9670.
12. (c) Li, J.; Worthington, S. E.; Cramer, C. J. J. Chem. Soc., Perkin Trans. 2 1998, 1045-1051.
13. (a) Slipchenko, L. V.; Krylov, A. I. J. Chem. Phys. 2002, 117, 4694-4708.
14. (b) Slipchenko, L. V.; Krylov, A. I. J. Chem. Phys. 2003, 118, 6874-6883.
15. Baily, T.; Maltsev, A.; Gerson, F.; Frank. D.; de Meijere. A. J. Am. Chem. Soc. 2005, 127, 1983-1988.
16. (a) Wenthold, P. G.; Hu, J.; Squires, R. R.; Lineberger, W. C. J. Am. Chem. Soc. 1996, 118, 475-476.
17. (b) Wenthold, P. G.; Hu, J.; Squires, R. R.; Lineberger, W. C. J. Am. Soc. Mass. Spectrom. 1999, 10, 800-809.
18. Radical cations of TMM in the gas phase: Chou, P. K.; Gao, L.; Tichy, S. E.; Painter, S. L.; Blackstock, S. C.; Kenttämaa, H. I. J. Phys. Chem. A 2000, 104, 5530-5534.
19. (a) Evans, W. J.; Perotti, J. M.; Ziller, J. W. J. Am. Chem. Soc. 2005. 127, 1068-1069.
20. (b) Kissounko, D. A.; Sita. L. R. J. Am. Chem. Soc. 2004, 126, 5946-5947.
21. (a) Maiti, A.; Gerken, J. B.; Masjedizadeh, M. R.; Mimieux, Y. S.; Little, R. D. J. Org. Chem. 2004, 69, 8574-8582.
22. (b) Lee, H.-Y.; Kim, Y. J. Am. Chem. Soc. 2003, 125, 10156-10157.
23. (c) Nakamura, E.; Yamago, S. Acc. Chem. Res. 2002, 35, 867-877.
24. (d) Trost, B. M.; Crawley, M. L. J. Am. Chem. Soc. 2002, 124, 9328-9329.
25. Reviews on high-spin polyradicals: (a) Iwamura, H.; Koga, N. Acc. Chem. Res. 1993, 26, 346-351.
26. (b) Rajca, A. Chem. Rev. 1994, 94, 871-893.
27. (c) Lahti, P. M. Magnetic Properties of Organic Materials: Marcel Dekker: New York. 1999; pp 1-713.
28. (d) Itoh, K., Kinoshita, M., Eds. Molecular Magnetism; Gordon and Breach: Kodansha. 2000; pp 1-337.
29. (e) Crayston, J. A.; Devine, J. N.; Walton, J. C. Tetrahedron 2000, 56. 7829-7857.
30. (f) Rajca, A. Chem.-Eur. J. 2002. 8, 4834-4841.
31. Bis-TMM tetraradicals: (a) Jacobs, S. J.; Shultz, D. A.; Jain, R.; Novak, J.; DouEherty, D. A. J. Am. Chem. Soc. 1993, 115, 1744-1753.
32. (b) Silverman, S. K.; Dougherty, D. A. J. Phys. Chem. 1993, 97, 13273-13283.
33. (c) West, A. P.; Jr.; Silverman, S. K.; Dousherty, D. A. J. Am. Chem. Soc. 1996, 118, 1452-1463.
34. (a) Tanaka, M.; Matsuda, K.; Itoh, T.; Iwamura, H. J. Am. Chem. Soc. 1998, 120, 7168-7173.
35. (b) Sakurai, H.; Izuoka, A.; Sugawara, T. J. Am. Chem. Soc. 2000, 122, 9723-9734.
36. (c) Shultz, D. A.; Fico, R. M.. Jr.; Bodnar, S. H.; Kumar, K.; Vostrikova, K. E.; Kampf, J. W.; Boyle, P. D. J. Am. Chem. Soc. 2003, 125, 11761-11771.
37. (d) Shultz, D. A.; Fico, R. M., Jr.; Lee, H.; Kampf. J. W.; Kirschbaum, K.; Pinkerton, A. A.; Boyle, P. D. J. Am. Chem. Soc. 2003, 125, 15426-15432.
38. Michinobu, T.; Inui, J.; Nishide, H. Org. Lett. 2003, 5, 2165-2168.
39. (a) Rajca, S.; Rajca, A.; Wongsriratanakul, J.; Butler, P.; Choi, S. J. Am. Chem. Soc. 2004, 126, 6972-6986.
40. (b) Rajca, A.; Wongsriratanakul. J.; Rajca, S. J. Am. Chem. Soc. 2004, 126, 6608-6626.
41. (c) Rajca, A.; Wongsriratanakul, J.; Rajca, S.; Cerny, R. L. Chem.-Eur. J. 2004, 10, 3144-3157.
42. (a) Rajca, A.; Wongsriratanakul, J.; Rajca, S. Science. 2001, 294, 1503-1505.
43. (b) Rajca, A.; Rajca, S.; Wongsriratanakul, J. J. Am. Chem. Soc. 1999, 727, 6308-6309.
44. Yang, N. C.; Castro, A. J. J. Am. Chem. Soc. 1960, 82, 6208-6208.
45. EPR spectroscopy and X-ray crystallography of 2: (a) Mukai, K.; Ishizu, K.; Kakahara, M.; Deguchi, Y. Bull. Chem. Soc. Jpn. 1980, 53, 3363-3364.
46. (b) Willigen, H.; Kirste, B.; Kurreck, H.; Plato, M. Tetrahedron 1982, 38, 759-764.
47. (c) Bock, H.; John, A.; Havlas, Z.; Bats, J. W. Angew. Chem., Int. Ed. Engl. 1993, 32, 416-418.
48. Tris[p-(N-oxyl-N-tert-butylamino)phenyl]methyl, diradical 3: (a) Itoh, T.; Matsuda, K.; Iwamura, H.; Hori, K. J. Am. Chem. Soc. 2000, 122, 2567-2576.
49. (b) Oniciu, D. C.; Matsuda, K.; Iwamura, H. J. Chem. Soc., Perkin 2 1996, 907-913.
50. Although extended high-spin structures can be drawn for analogues of 3, in which t-Bu groups are replaced with 1,3-phenylene-like coupling units, such oligonitroxides would be unprecedented. For example, no successful extension from diarylnitroxide to high-spin π-conjugated bis(diarylnitroxides) was reported to date.
51. The diradical, which is formally derived from 2 via replacement of one of the phenoxyls with the triarylmethyl, was difficult to prepare, and neither its ground state nor strength of the exchange coupling could be determined: Fukuzaki, E.; Takahashi, N.; Imai, S.; Nishide, H.; Rajca, A. Polym. J. 2005, 37, 284-293.
52. Rajca, A.; Utamapanya, S. J. Org. Chem. 1992, 57, 1760-1767.
53. Rajca, A. J. Org. Chem. 1991, 56, 2557-2563.
54. Utamapanya, S.; Rajca, A. J. Am. Chem. Soc. 1991, 113, 9242-9251.
55. Bard, A. J.; Faulkner, L. R. Electrochemical Methods: Wiley: New York. 1980; Chapters 3, 11, and 12.
56. 6 (or inadvertent protic impurities).
57. (a) Rajca, S.; Rajca, A. J. Am. Chem. Soc. 1995, 117, 9172-9179.
58. (b) Rajca, A.; Rajca, S.; Desai, S. R. J. Am. Chem. Soc. 1995, 117, 806-816.
59. 1 is confirmed, using partially refined X-ray crystallographic data (Figure 2s, Supporting Information).
60. Rajca, A.; Safronov, A.; Rajca, S.; Wongsriratanakul, J. J. Am. Chem. Soc. 2000, 122, 3351-3357.
61. Sommerfeld, T. J. Am. Chem. Soc. 2002, 124, 1119-1124.
62. Connelly, N. G.; Geiger, W. E. Chem. Rev. 1996, 96, 877-910.
63. The g value for 1 is approximately 2.003.
64. 19b
65. Wertz, J. E.; Bolton, J. R. Electron Spin Resonance; Chapman and Hall: New York, 1986; Chapter 10, pp 242-244.
66. Because the samples are relatively short (∼5 mm height), the spectra are dependent on the position of the sample tube in the X-band cavity; that is, a relatively more intense center line is obtained when the upper part of the sample tube (especially just above the sample) is inside the cavity. This part of the sample tube is more likely to contain "impurities" (e.g., monoradicals, precipitated diradical) and also diradical, which could have been inadvertently warmed during the preparation.
67. 15
68. Anderson, P. W.; Weiss, P. R. Rev. Mod. Phys. 1953, 25, 269-276.
69. Blue solutions of 1 in 2-MeTHF/THF are prepared via oxidation of the carbotetraanion in THF at -78°C, followed by dilution with 2-MeTHF and annealing at room temperature; the EPR spectra, such as in Figure 6, were obtained as early as in 1991. However, at that time, the techniques for SQUID sample preparation were not developed to allow for quantitative magnetic measurements of air-sensitive liquid samples, as reported in this work.
70. Approximately zero value E/hc may also be found by accident, for example, ref 2c.
71. 3, where r is the distance between point dipoles: Rohde, O.; Van, S. P.; Rester, W. R.; Griffith, O. H. J. Am. Chem. Soc. 1974, 96, 5311-5318.