Interconversion between Bis(μ-thiolato)dicopper(II) and disulfide-bridged dicopper(I) complexes mediated by chloride ion

Journal of the American Chemical Society

Volumn 124, Issue 42, 2002, Pages 12428-12429

  Ueno, Yoshiki ^a   Tachi, Yoshimitsu ^a   Itoh, Shinobu ^a  

^a Osaka Prefecture University   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

BIS(MU THIOLATO)DICOPPER; CHLORIDE ION; COPPER COMPLEX; DISULFIDE; LIGAND; OXYGEN; SULFUR; UNCLASSIFIED DRUG;

ARTICLE; CATALYST; CHEMICAL REACTION; CHEMICAL STRUCTURE; CRYSTAL STRUCTURE; OXIDATION REDUCTION REACTION; SPECTRUM;

EID: 0037164049     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja027397m     Document Type: Article

References (25)

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5. There has been speculation on this type of thiolate-disulfide interconversion for more than 50 years, and the problem has been discussed on the basis of the results of kinetic studies; see, Lappin A. G.; McAuley, A. J. Chem. Soc., Dalton Trans. 1978, 1606-1609 and references therein. However, no structural evidence on this issue has ever been reported thus far.
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14. Synthetic procedures for the ligand and copper complexes as well as the analytical data of the products are presented in Supporting Information.
15. There are two independent molecules of compound 1 in the unit cell of the single crystal (see. Table S2 and CIF file).
16. CIO4 = 2.93 and 3.07 Å for the two independent molecules of 1, respectively).
17. 1H NMR signals of 1 appear within a range between δ 1.8-16.0, indicating the antiferromagnetic nature of the dicopper(II) complex. Detailed signal assignment was, however, hampered by significant broadening of the signals.
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19. Complex 1 exhibits reduction peaks at -0.17 and -0.49 V and oxidation peaks at 0.08 and -0.30 V vs ferrocene/ferrocenium (Figure S2). These peaks may correspond to the redox couples of Cu(II)Cu(II)/CuCu(II) and Cu(I) Cu(II)/Cu(I)Cu(I) of the dicopper complex, respectively
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22. In support of the proposed structure of 2, the disulfide-bridged (μ-chloro)-dicopper complex has been obtained using a very similar disulfide ligand (2L′); see Supporting Information (Tables S2 and S4).
23. 4 into acetone, a small amount of 18-crown-6 was added.
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