Bis[1,2,3,4,5,6,7,8-octahydro-1,4:5,8-di(ethano)anthryl]carbene. the first all-hydrocarbon triplet diphenylcarbene having a half-life over one second under normal conditions

Chemical Communications

Volumn , Issue 23, 1997, Pages 2261-2262

  Tomioka, Hideo ^a   Mizuno, Hidehiko ^a   Itakura, Hidetaka ^a   Hirai, Katsuyuki ^a  

^a MIE UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0037969275     PISSN: 13597345     EISSN: None     Source Type: Journal    
DOI: 10.1039/a706663e     Document Type: Article

References (23)

1. The first attempts to isolate triplet carbenes were made by Zimmerman and Paskovich: H. E. Zimmerman and D. H. Paskovich, J. Am. Chem. Soc., 1984, 88, 5251.
2. A. Igau, H. Grützmacher, A. Baceiredo and G. Bertrand, J. Am. Chem. Soc., 1988, 110, 6463;
3. see also: M. Soleilhavoup, A. Baceiredo, O. Treutler, R. Ahlichs, M. Nieger and G. Bertrand, ibid., 1992, 114, 10959 and references cited therein.
4. A. J. Arduengo, III, R. L. Harlow and M. Kline, J. Am. Chem. Soc., 1991, 113, 361;
5. see also: A. J. Arduengo, III, J. R. Goerlich and W. J. Marshall, ibid., 1995, 117, 11 027 and references cited therein.
6. For discussion of the electronic structure for those stable singlet carbenes, see C. Heinemann, T. Müller, Y. Apeloig and H. Schwarz, J. Am. Chem. Soc., 1996, 118, 2039.
7. (a) H. Tomioka, H. Okada, T. Watanabe and K. Hirai, Angew. Chem., Int. Ed. Engl., 1994, 33, 873;
8. (b) K. Hirai, K. Komatsu and H. Tomioka, Chem. Lett., 1994, 503;
9. (c) K. Furukawa, Y. Teki, T. Takui, K. Itoh, T. Watanabe, K. Hirai and H. Tomioka, Mol. Cryst. Liq. Cryst., 1995, 271, 183;
10. H. Tomioka, H. Okada, T. Watanabe, K. Banno, K. Komatsu and K. Hirai, J. Am. Chem. Soc., 1997, 119, 1582.
11. H. Tomioka, K. Hirai and C. Fujii, Acta Chem. Scand., 1992, 46, 680;
12. H. Tomioka, K. Hirai and T. Nakayama, J. Am. Chem. Soc., 1993, 115, 1285.
13. H. Tomioka, T. Watanabe, K. Hirai, K. Furukawa, T. Takui and K. Itoh, J. Am. Chem. Soc., 1995, 117, 6376;
14. H. Tomioka, M. Hattori, K. Hirai and S. Murata, ibid., 1996, 118, 8723.
15. V. R. Koch and G. J. Cleicher, J. Am. Chem. Soc., 1971, 93, 1657 and references cited therein.
16. For a recent review of EPR data of triplet arylcarbenes, see W. Sander, G. Bucher and S. Wievlacher, Chem. Rev., 1993, 93, 1583.
17. The optical absorption spectra of several aromatic carbenes in frozen media have been assigned: A. M. Trozzolo and E. Wasserman, in Carbenes, ed. R. A. Moss and M. Jones, Jr., Wiley, New York, 1975, vol. 2, pp. 185-206.
18. For review, see M. S. Platz and V. M. Maloney, in Kinetics and Spectroscopy of Carbenes and Biradicals, ed. M. S. Platz, Plenum, New York, 1990, pp. 239-352;
19. J. E. Jackson and M. S. Platz, in Advances in Carbene Chemistry, ed. U. Brinker, JAI, Greenwich, CT, 1994, vol. 1, pp. 87-160.
20. It is well-documented that diarylcarbenes with triplet ground states are readily trapped by oxygen to generated the corresponding diary ketone oxides. For a review, see W. W. Sander, Angew. Chem., Int. Ed. Engl., 1990, 29, 344;
21. see also J. C. Scaiano, W. G. McGimpsey and H. L. Casal, J. Org. Chem., 1989, 54, 1612.
22. J. J. P. Stewart, J. Comput. Chem., 1989, 10, 209, 221;
23. MOPAC version 6.01 (JCPE No. P044) was used.