Synthesis, structure and reactivity of phenoxo copper(II) complexes, Cu(OAr)(HB(3,5-Pri2pz)3) (Ar = C6H4-4-F, 2,6-Me2C6H3, 2,6-But2C6H3)

Chemistry Letters

Volumn , Issue 8, 1999, Pages 739-740

  Fujisawa, Kiyoshi ^c   Iwata, Yusaku ^a   Kitajima, Nobumasa ^a   Higashimura, Hideyuki ^b   Kubota, Masaaki ^b   Miyashita, Yoshitaro ^c   Yamada, Yasunori ^c   Okamoto, Ken Ichi ^c   Moro Oka, Yoshihiko ^a  

^a TOKYO INSTITUTE OF TECHNOLOGY   (Japan)

^b JAPAN CHEMICAL INNOVATION INSTITUTE   (Japan)

^c UNIVERSITY OF TSUKUBA   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0033471713     PISSN: 03667022     EISSN: None     Source Type: Journal    
DOI: 10.1246/cl.1999.739     Document Type: Article

References (20)

1. Copper is known as an effective catalyst for oxidative coupling reactions of phenols with dioxygen. The reaction has been explained in terms of free-radical mechanism involving a phenoxo radical, however, the details of the initial mechanism for the formation of the radical from phenol/dioxygen/copper has not been clarified yet.: A. S. Hay, J. Polym. Sci., Polym. Chem. Ed., 36, 505 (1998).
2. a) K. Lerch, Methods Enzymol., 142, 165 (1987).
3. b) R. S. Himmelwrght, N. C. Eickman, C. D. LuBien, K. Lerch, and E. I. Solomon, J. Am. Chem. Soc., 102, 7339 (1980).
4. a) E. I. Solomon, U. M. Sundaram, and T. E. Machonkin, Chem. Rev., 96, 2563 (1996).
5. b) W. B. Tolman, Acc. Chem. Res., 30, 227 (1997).
6. M. S. Nasir, B. I. Cohen, and K. D. Karlin, J. Am. Chem. Soc., 114, 2482 (1992).
7. a) N. Kitajima and Y. Moro-oka, Chem. Rev., 94, 737 (1994).
8. b) N. Kitajima, T. Koda, Y. Iwata, and Y. Moro-oka, J. Am. Chem. Soc., 112, 8833 (1990).
9. N. Kitajima, K. Fujisawa, C. Fujimoto, Y. Moro-oka, S. Hashimoto, T. Kitagawa, K. Toriumi, K. Tatsumi, and A. Nakamura, J. Am. Chem. Soc., 114, 1277 (1992).
10. 2 peroxo copper(II) complexes are effective for the polymerization of phenols. H. Higashimura, K. Fujisawa, Y. Moro-oka, M. Kubota, A. Terahara, A. Shiga, H. Uyama, and S. Kobayashi, J. Am. Chem. Soc., 120, 8529 (1998).
11. 3) 310(4450), 345(3230), 568 (1520), 833(3070).
12. -1, 2θmax = 50.0 °, T = -60 °C. Of 63760 unique reflections measured, 3480 [I > 5.0 σ(I)] were used in refinement (R = 0.045, Rw = 0.030).
13. a) Y. Wang, J. L. DuBois, B. Hedman, K. O. Hodgson, and T. D. P. Stack, Science, 279, 537 (1998).
14. b) K. A. Sokolowski, H. Leutbecher, T. Weyhermüller, R. Schnepf, E. Bothe, E. Bill, P. Hildebrandt, and K. Wieghardt, J. Biol. Inorg. Chem., 2, 444 (1997).
15. J. A. Halfen, B. A. Jazdzeweski, S. Mahapatra, L. M. Berreau, E. C. Wilkinson, L. Que Jr., and W. B. Tolman, J. Am. Chem. Soc., 119, 8217 (1997).
16. N. Kitajima, K. Fujisawa, and Y. Moro-oka, J. Am. Chem. Soc., 112, 3210 (1990).
17. N. Kitajima, T. Katayama, K. Fujisawa, Y. Iwata, and Y. Moro-oka, J. Am. Chem. Soc., 115, 7872 (1993).
18. The complex 2 a is very stable because of 4-F substitution. In the same reaction condition, the characteristic absorption bands did not decline.
19. 2. The atmosphere was replaced with argon or dioxygen and the solution was allowed to stand at room temperature for one hour.
20. In tyrosinase, only one phenol (tyrosine) can be inserted into the substrate binding pocket in the protein, so the initial intermediate is most likely this mononuclear phenoxo copper(II) intermediate.