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Volumn 120, Issue 12, 1998, Pages 2890-2899

Mechanistic studies of aliphatic ligand hydroxylation of a copper complex by dioxygen: A model reaction for copper monooxygenases

Author keywords

[No Author keywords available]

Indexed keywords

COPPER COMPLEX; OXYGEN; UNSPECIFIC MONOOXYGENASE;

EID: 0032053562     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja972809q     Document Type: Article
Times cited : (143)

References (87)
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    • A superoxocopper(II) complex with a end-on fashion was reported by Harata et al. (Harata, M.; Jitsukawa, K.; Masuda, H.; Einaga, H. J. Am. Chem. Soc. 1994, 116, 10817), but its structure has been recently claimed to be questionable by Berreau et al. (Berreau, L. M.; Mahapatra, S.; Halfen, J. A.; Young, V. G., Jr.; Tolman, W. B. Inorg. Chem. 1996, 35, 6339).
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    • A superoxocopper(II) complex with a end-on fashion was reported by Harata et al. (Harata, M.; Jitsukawa, K.; Masuda, H.; Einaga, H. J. Am. Chem. Soc. 1994, 116, 10817), but its structure has been recently claimed to be questionable by Berreau et al. (Berreau, L. M.; Mahapatra, S.; Halfen, J. A.; Young, V. G., Jr.; Tolman, W. B. Inorg. Chem. 1996, 35, 6339).
    • (1996) Inorg. Chem. , vol.35 , pp. 6339
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    • note
    • Crystal structures of the copper(II) complex I and dimeric copper-(II) complex J of the hydroxylated ligand 2a (Scheme 3) have been reported in ref 22.
  • 63
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    • Réglier et al. reported that the ligand hydroxylation occurs only at the o-position of one pyridine nucleus in the reaction of Cu(I) complex of the same ligand 1a with iodosylbenzene: Réglier, M.; Amadeï, E.; Tadayoni, R.; Waegell, B. J. Chem. Soc., Chem. Commun. 1989, 447.
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    • Itoh, S.; Nakao, H.; Fukuzumi, S.; Mukai, M.; Kitagawa, T. Unpublished results
    • High reactivity of the μ-peroxodicopper(II) complex has precluded getting a solution resonance Raman spectrum at -80°C: Itoh, S.; Nakao, H.; Fukuzumi, S.; Mukai, M.; Kitagawa, T. Unpublished results.
  • 66
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    • note
    • Direct injection of a concentrated solution of the Cu(I) starting materials into the solvent saturated with dioxygen at the low temperature may remove the lag phase observed in Figure 3, enabling us to detect the initially formed Cu(I)-superoxo intermediate (Scheme 4). However, the limited solubility of the Cu(I) starting materials in THF has precluded doing this experiment.
  • 71
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    • note
    • 2-binding at higher temperature (>-40 °C).
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    • 30a This is reasonable since the electrophilic attack of the peroxo species upon the proximate aromatic substrate is the rate-determining step in their system: Nasir, M. S.; Cohen, B. I.; Karlin, K. D. J. Am. Chem. Soc. 1992, 114, 2482.
    • (1992) J. Am. Chem. Soc. , vol.114 , pp. 2482
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    • note
    • 15
  • 75
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    • note
    • The electron-donating substituent would increase the d-π interaction between the copper center and the benzene ring, which may prevent the interaction of the copper center with dioxygen by a steric hindrance. Details about such interaction in the copper complexes will be reported elsewhere.
  • 77
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    • note
    • In this paper, the monomeric species formed from the peroxo intermediate by O-O bond homolysis is described as Cu(II)-O·, although another canonical form Cu(III)=O is also possible. In the present system, however, we could not characterize such a monomeric copper-oxygen species, since it is just a transient reactive intermediate, if it is formed.
  • 78
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    • note
    • 2-peroxodicopper(II) species.
  • 79
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    • note
    • 18
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    • and references therein
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