Of ortho-conjugatively linked reactive intermediates: The cases of ortho-phenylene-(bis)nitrene, -carbenonitrene, and -(bis)carbene

Journal of the American Chemical Society

Volumn 121, Issue 45, 1999, Pages 10563-10572

  Nicolaides, Athanassios ^a   Nakayama, Takehito ^a   Yamazaki, Katsuhisa ^a   Tomioka, Hideo ^a   Koseki, Shiro ^a   Stracener, Louise L ^b   McMahon, Robert J ^b  

^a MIE UNIVERSITY   (Japan)

^b UNIVERSITY OF WISCONSIN MADISON   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKADIENE; CYCLOALKENE; RADICAL;

ARTICLE; CALCULATION; CONJUGATION; CYCLIZATION; INFRARED SPECTROSCOPY; PHOTOCHEMISTRY; STEREOCHEMISTRY; SYNTHESIS; TEMPERATURE DEPENDENCE;

EID: 0033579138     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja9913636     Document Type: Article

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13. For dinitrenes conjugatively connected through benzene ring, see: (a) Singh, B.; Brinen, J. J. Am. Chem. Soc. 1971, 93, 540. (b) Yabe, A. Bull. Chem. Soc. Jpn. 1980, 53, 2933. (c) Ohana, T.; Ouchi, A.; Moriyama, H.; Yabe, A. J. Photochem. Photobiol., A 1993, 72, 83. (d) Ohana, T.; Kaise, M.; Yabe, A. Chem. Lett. 1992, 1397. (e) Ohana, T.; Kaise, M.; Mimura, S.; Kikuchi, O.; Yabe, A. Chem. Lett. 1993, 765. (f) Ling, C.; Lahti, P. M. Chem. Lett. 1993, 769. (g) Minato, M.; Lahti, P. M.; van Willigen, H. J. Am. Chem. Soc. 1993, 115, 4532. (h) Ichimura, A. S.; Lahti, P. M. Mol. Cryst. Liq. Cryst. 1993, 233, 33. (i) Minato. M.; Lahti, P. M. J. Phys. Org. Chem. 1993, 6, 483. (j) Harder, T.; Bendig, J.; Scholz, G.; Stösser, R. J. Am. Chem. Soc. 1996, 118, 2497. (k) Nimura, S.; Kikuchi, O.; Ohana, T.; Yabe, A.; Kaise, M. Chem. Lett. 1996, 125.
14. For dinitrenes conjugatively connected through benzene ring, see: (a) Singh, B.; Brinen, J. J. Am. Chem. Soc. 1971, 93, 540. (b) Yabe, A. Bull. Chem. Soc. Jpn. 1980, 53, 2933. (c) Ohana, T.; Ouchi, A.; Moriyama, H.; Yabe, A. J. Photochem. Photobiol., A 1993, 72, 83. (d) Ohana, T.; Kaise, M.; Yabe, A. Chem. Lett. 1992, 1397. (e) Ohana, T.; Kaise, M.; Mimura, S.; Kikuchi, O.; Yabe, A. Chem. Lett. 1993, 765. (f) Ling, C.; Lahti, P. M. Chem. Lett. 1993, 769. (g) Minato, M.; Lahti, P. M.; van Willigen, H. J. Am. Chem. Soc. 1993, 115, 4532. (h) Ichimura, A. S.; Lahti, P. M. Mol. Cryst. Liq. Cryst. 1993, 233, 33. (i) Minato. M.; Lahti, P. M. J. Phys. Org. Chem. 1993, 6, 483. (j) Harder, T.; Bendig, J.; Scholz, G.; Stösser, R. J. Am. Chem. Soc. 1996, 118, 2497. (k) Nimura, S.; Kikuchi, O.; Ohana, T.; Yabe, A.; Kaise, M. Chem. Lett. 1996, 125.
15. For dinitrenes conjugatively connected through benzene ring, see: (a) Singh, B.; Brinen, J. J. Am. Chem. Soc. 1971, 93, 540. (b) Yabe, A. Bull. Chem. Soc. Jpn. 1980, 53, 2933. (c) Ohana, T.; Ouchi, A.; Moriyama, H.; Yabe, A. J. Photochem. Photobiol., A 1993, 72, 83. (d) Ohana, T.; Kaise, M.; Yabe, A. Chem. Lett. 1992, 1397. (e) Ohana, T.; Kaise, M.; Mimura, S.; Kikuchi, O.; Yabe, A. Chem. Lett. 1993, 765. (f) Ling, C.; Lahti, P. M. Chem. Lett. 1993, 769. (g) Minato, M.; Lahti, P. M.; van Willigen, H. J. Am. Chem. Soc. 1993, 115, 4532. (h) Ichimura, A. S.; Lahti, P. M. Mol. Cryst. Liq. Cryst. 1993, 233, 33. (i) Minato. M.; Lahti, P. M. J. Phys. Org. Chem. 1993, 6, 483. (j) Harder, T.; Bendig, J.; Scholz, G.; Stösser, R. J. Am. Chem. Soc. 1996, 118, 2497. (k) Nimura, S.; Kikuchi, O.; Ohana, T.; Yabe, A.; Kaise, M. Chem. Lett. 1996, 125.
16. For dinitrenes conjugatively connected through benzene ring, see: (a) Singh, B.; Brinen, J. J. Am. Chem. Soc. 1971, 93, 540. (b) Yabe, A. Bull. Chem. Soc. Jpn. 1980, 53, 2933. (c) Ohana, T.; Ouchi, A.; Moriyama, H.; Yabe, A. J. Photochem. Photobiol., A 1993, 72, 83. (d) Ohana, T.; Kaise, M.; Yabe, A. Chem. Lett. 1992, 1397. (e) Ohana, T.; Kaise, M.; Mimura, S.; Kikuchi, O.; Yabe, A. Chem. Lett. 1993, 765. (f) Ling, C.; Lahti, P. M. Chem. Lett. 1993, 769. (g) Minato, M.; Lahti, P. M.; van Willigen, H. J. Am. Chem. Soc. 1993, 115, 4532. (h) Ichimura, A. S.; Lahti, P. M. Mol. Cryst. Liq. Cryst. 1993, 233, 33. (i) Minato. M.; Lahti, P. M. J. Phys. Org. Chem. 1993, 6, 483. (j) Harder, T.; Bendig, J.; Scholz, G.; Stösser, R. J. Am. Chem. Soc. 1996, 118, 2497. (k) Nimura, S.; Kikuchi, O.; Ohana, T.; Yabe, A.; Kaise, M. Chem. Lett. 1996, 125.
17. For dinitrenes conjugatively connected through benzene ring, see: (a) Singh, B.; Brinen, J. J. Am. Chem. Soc. 1971, 93, 540. (b) Yabe, A. Bull. Chem. Soc. Jpn. 1980, 53, 2933. (c) Ohana, T.; Ouchi, A.; Moriyama, H.; Yabe, A. J. Photochem. Photobiol., A 1993, 72, 83. (d) Ohana, T.; Kaise, M.; Yabe, A. Chem. Lett. 1992, 1397. (e) Ohana, T.; Kaise, M.; Mimura, S.; Kikuchi, O.; Yabe, A. Chem. Lett. 1993, 765. (f) Ling, C.; Lahti, P. M. Chem. Lett. 1993, 769. (g) Minato, M.; Lahti, P. M.; van Willigen, H. J. Am. Chem. Soc. 1993, 115, 4532. (h) Ichimura, A. S.; Lahti, P. M. Mol. Cryst. Liq. Cryst. 1993, 233, 33. (i) Minato. M.; Lahti, P. M. J. Phys. Org. Chem. 1993, 6, 483. (j) Harder, T.; Bendig, J.; Scholz, G.; Stösser, R. J. Am. Chem. Soc. 1996, 118, 2497. (k) Nimura, S.; Kikuchi, O.; Ohana, T.; Yabe, A.; Kaise, M. Chem. Lett. 1996, 125.
18. For dinitrenes conjugatively connected through benzene ring, see: (a) Singh, B.; Brinen, J. J. Am. Chem. Soc. 1971, 93, 540. (b) Yabe, A. Bull. Chem. Soc. Jpn. 1980, 53, 2933. (c) Ohana, T.; Ouchi, A.; Moriyama, H.; Yabe, A. J. Photochem. Photobiol., A 1993, 72, 83. (d) Ohana, T.; Kaise, M.; Yabe, A. Chem. Lett. 1992, 1397. (e) Ohana, T.; Kaise, M.; Mimura, S.; Kikuchi, O.; Yabe, A. Chem. Lett. 1993, 765. (f) Ling, C.; Lahti, P. M. Chem. Lett. 1993, 769. (g) Minato, M.; Lahti, P. M.; van Willigen, H. J. Am. Chem. Soc. 1993, 115, 4532. (h) Ichimura, A. S.; Lahti, P. M. Mol. Cryst. Liq. Cryst. 1993, 233, 33. (i) Minato. M.; Lahti, P. M. J. Phys. Org. Chem. 1993, 6, 483. (j) Harder, T.; Bendig, J.; Scholz, G.; Stösser, R. J. Am. Chem. Soc. 1996, 118, 2497. (k) Nimura, S.; Kikuchi, O.; Ohana, T.; Yabe, A.; Kaise, M. Chem. Lett. 1996, 125.
19. For dinitrenes conjugatively connected through benzene ring, see: (a) Singh, B.; Brinen, J. J. Am. Chem. Soc. 1971, 93, 540. (b) Yabe, A. Bull. Chem. Soc. Jpn. 1980, 53, 2933. (c) Ohana, T.; Ouchi, A.; Moriyama, H.; Yabe, A. J. Photochem. Photobiol., A 1993, 72, 83. (d) Ohana, T.; Kaise, M.; Yabe, A. Chem. Lett. 1992, 1397. (e) Ohana, T.; Kaise, M.; Mimura, S.; Kikuchi, O.; Yabe, A. Chem. Lett. 1993, 765. (f) Ling, C.; Lahti, P. M. Chem. Lett. 1993, 769. (g) Minato, M.; Lahti, P. M.; van Willigen, H. J. Am. Chem. Soc. 1993, 115, 4532. (h) Ichimura, A. S.; Lahti, P. M. Mol. Cryst. Liq. Cryst. 1993, 233, 33. (i) Minato. M.; Lahti, P. M. J. Phys. Org. Chem. 1993, 6, 483. (j) Harder, T.; Bendig, J.; Scholz, G.; Stösser, R. J. Am. Chem. Soc. 1996, 118, 2497. (k) Nimura, S.; Kikuchi, O.; Ohana, T.; Yabe, A.; Kaise, M. Chem. Lett. 1996, 125.
20. For dinitrenes conjugatively connected through benzene ring, see: (a) Singh, B.; Brinen, J. J. Am. Chem. Soc. 1971, 93, 540. (b) Yabe, A. Bull. Chem. Soc. Jpn. 1980, 53, 2933. (c) Ohana, T.; Ouchi, A.; Moriyama, H.; Yabe, A. J. Photochem. Photobiol., A 1993, 72, 83. (d) Ohana, T.; Kaise, M.; Yabe, A. Chem. Lett. 1992, 1397. (e) Ohana, T.; Kaise, M.; Mimura, S.; Kikuchi, O.; Yabe, A. Chem. Lett. 1993, 765. (f) Ling, C.; Lahti, P. M. Chem. Lett. 1993, 769. (g) Minato, M.; Lahti, P. M.; van Willigen, H. J. Am. Chem. Soc. 1993, 115, 4532. (h) Ichimura, A. S.; Lahti, P. M. Mol. Cryst. Liq. Cryst. 1993, 233, 33. (i) Minato. M.; Lahti, P. M. J. Phys. Org. Chem. 1993, 6, 483. (j) Harder, T.; Bendig, J.; Scholz, G.; Stösser, R. J. Am. Chem. Soc. 1996, 118, 2497. (k) Nimura, S.; Kikuchi, O.; Ohana, T.; Yabe, A.; Kaise, M. Chem. Lett. 1996, 125.
21. For analogous studies on dicarbenes, see: (a) Sixl, H.; Mathes, R.; Schaupp, A.; Ulrich, K. Chem. Phys. 1986, 107, 105. (b) Zuev, P.; Sheridan, R. S. J. Am. Chem. Soc. 1993, 115, 3788. (c) Tomioka, H.; Komatsu, K.; Nakayama, T.; Shmizu, M. Chem. Lett. 1993, 1291. (d) Zuev, P.; Sheridan, R. S. J. Am. Chem. Soc. 1994, 116, 9381. (e) Ohana, T.; Yabe, A. IUPAC Symposium on Photochemistry; July 1994, Prague, Czeck, 1994; p 351.
22. For analogous studies on dicarbenes, see: (a) Sixl, H.; Mathes, R.; Schaupp, A.; Ulrich, K. Chem. Phys. 1986, 107, 105. (b) Zuev, P.; Sheridan, R. S. J. Am. Chem. Soc. 1993, 115, 3788. (c) Tomioka, H.; Komatsu, K.; Nakayama, T.; Shmizu, M. Chem. Lett. 1993, 1291. (d) Zuev, P.; Sheridan, R. S. J. Am. Chem. Soc. 1994, 116, 9381. (e) Ohana, T.; Yabe, A. IUPAC Symposium on Photochemistry; July 1994, Prague, Czeck, 1994; p 351.
23. For analogous studies on dicarbenes, see: (a) Sixl, H.; Mathes, R.; Schaupp, A.; Ulrich, K. Chem. Phys. 1986, 107, 105. (b) Zuev, P.; Sheridan, R. S. J. Am. Chem. Soc. 1993, 115, 3788. (c) Tomioka, H.; Komatsu, K.; Nakayama, T.; Shmizu, M. Chem. Lett. 1993, 1291. (d) Zuev, P.; Sheridan, R. S. J. Am. Chem. Soc. 1994, 116, 9381. (e) Ohana, T.; Yabe, A. IUPAC Symposium on Photochemistry; July 1994, Prague, Czeck, 1994; p 351.
24. For analogous studies on dicarbenes, see: (a) Sixl, H.; Mathes, R.; Schaupp, A.; Ulrich, K. Chem. Phys. 1986, 107, 105. (b) Zuev, P.; Sheridan, R. S. J. Am. Chem. Soc. 1993, 115, 3788. (c) Tomioka, H.; Komatsu, K.; Nakayama, T.; Shmizu, M. Chem. Lett. 1993, 1291. (d) Zuev, P.; Sheridan, R. S. J. Am. Chem. Soc. 1994, 116, 9381. (e) Ohana, T.; Yabe, A. IUPAC Symposium on Photochemistry; July 1994, Prague, Czeck, 1994; p 351.
25. For analogous studies on dicarbenes, see: (a) Sixl, H.; Mathes, R.; Schaupp, A.; Ulrich, K. Chem. Phys. 1986, 107, 105. (b) Zuev, P.; Sheridan, R. S. J. Am. Chem. Soc. 1993, 115, 3788. (c) Tomioka, H.; Komatsu, K.; Nakayama, T.; Shmizu, M. Chem. Lett. 1993, 1291. (d) Zuev, P.; Sheridan, R. S. J. Am. Chem. Soc. 1994, 116, 9381. (e) Ohana, T.; Yabe, A. IUPAC Symposium on Photochemistry; July 1994, Prague, Czeck, 1994; p 351.
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42. See for example: (a) Johnson, B. G.; Gill, P. M. W.; Pople, J. A. J. Chem. Phys. 1993, 98, 5612. (b) Handy, N. C.; Murray, C. W.; Amos, R. D. J. Phys. Chem. 1993, 97, 4392. (c) Stephens, B. J.; Devlin, I. J.; Chabalowsky, C, F.; Frisch, M. J. J. Phys. Chem. 1994, 98, 11623. (d) Choi, C. H.; Kertesz, M. J. Phys. Chem. 1996, 100, 16530.
43. See for example: (a) Johnson, B. G.; Gill, P. M. W.; Pople, J. A. J. Chem. Phys. 1993, 98, 5612. (b) Handy, N. C.; Murray, C. W.; Amos, R. D. J. Phys. Chem. 1993, 97, 4392. (c) Stephens, B. J.; Devlin, I. J.; Chabalowsky, C, F.; Frisch, M. J. J. Phys. Chem. 1994, 98, 11623. (d) Choi, C. H.; Kertesz, M. J. Phys. Chem. 1996, 100, 16530.
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45. For some examples of DFT calculations on open-shell singlets see: (a) Cramer, C. J.; Dulles, F. J.; Giesen, D. J.; Almlöf, J. Chem. Phys. Lett. 1995, 245, 165. (b) Schreiner, P. J. Am. Chem. Soc. 1998, 120, 4184. (c) Marquardt, R.; Balster, A.; Sander, W.; Kraka, E.; Cremer, D.; Radziszewski, J. G. Angew. Chem., Int. Ed. Engl. 1998, 37, 955.
46. For some examples of DFT calculations on open-shell singlets see: (a) Cramer, C. J.; Dulles, F. J.; Giesen, D. J.; Almlöf, J. Chem. Phys. Lett. 1995, 245, 165. (b) Schreiner, P. J. Am. Chem. Soc. 1998, 120, 4184. (c) Marquardt, R.; Balster, A.; Sander, W.; Kraka, E.; Cremer, D.; Radziszewski, J. G. Angew. Chem., Int. Ed. Engl. 1998, 37, 955.
47. Preliminary MCSCF calculations on these systems have been reported previously, with similar results. (a) Koseki, S.; Tomioka, H.; Toyota, A. J. Phys. Chem. 1994, 98, 13203. (b) Koseki, S.; Tomioka, H.; Yamazaki, K.; Toyota, A. J. Phys. Chem. 1997, 101, 3377.
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49. 17 In the present systems, since the singlet and triplet biradicals have the same molecular orbital occupancies, this may be less of a problem. However, the quintet states, which have a different number of a electrons in the π space, may be favored energetically.
50. As for example is the case with the S-T splitting of phenyl cation: Nicolaides, A.; Smith, D. M.; Jensen, F.; Radom, L. J Am. Chem. Soc. 1997, 119, 8083.
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