A thiolate-bridged, fully delocalized mixed-valence dicopper(I,II) complex that models the CuA biological electron-transfer site

Journal of the American Chemical Society

Volumn 118, Issue 8, 1996, Pages 2101-2102

  Houser, Robert P ^a   Young Jr , Victor G ^a   Tolman, William B ^a  

^a University of Minnesota   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

COPPER COMPLEX;

ARTICLE; CRYSTALLOGRAPHY; DRUG STRUCTURE; ELECTRON SPIN RESONANCE; ELECTRON TRANSPORT; MOLECULAR DYNAMICS; SPECTROPHOTOMETRY;

EID: 0029874826     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja953776m     Document Type: Article

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22. Mixed-valence multicopper complexes usually are completely valence localized (class I), but in some instances spectroscopic evidence for delocalization of unpaired spin in a binuclear complex or dicopper protein active site. usually at elevated temperatures (>77 K), has been observed (class II behavior) For examples, see: (a) Dunaj-Jurco, M.; Ondrejovic, G.; Melnik, M. Coord. Chem. Rev. 1988, 83, 1-28 (b) Long, R. C.; Hendrickson, D. N. J. Am. Chem. Soc. 1983, 105, 1513-1521. (c) Gagné, R. R.; Koval, C. A.; Smith, T. J.; Cimolino, M. C J. Am. Chem. Soc. 1979, 101, 4571-4580. (d) Westmoreland, T. D.; Wilcox, D. E.; Baldwin, M. J.; Mims, W. B.; Solomon, E. I. J. Am. Chem. Soc. 1989, 111, 6106-6123 (e) Aasa, R.; Deinum, J.; Lerch, K.; Reinhammar B. Biochim. Biophys. Acta 1978, 535, 287-298.
23. Mixed-valence multicopper complexes usually are completely valence localized (class I), but in some instances spectroscopic evidence for delocalization of unpaired spin in a binuclear complex or dicopper protein active site. usually at elevated temperatures (>77 K), has been observed (class II behavior) For examples, see: (a) Dunaj-Jurco, M.; Ondrejovic, G.; Melnik, M. Coord. Chem. Rev. 1988, 83, 1-28 (b) Long, R. C.; Hendrickson, D. N. J. Am. Chem. Soc. 1983, 105, 1513-1521. (c) Gagné, R. R.; Koval, C. A.; Smith, T. J.; Cimolino, M. C J. Am. Chem. Soc. 1979, 101, 4571-4580. (d) Westmoreland, T. D.; Wilcox, D. E.; Baldwin, M. J.; Mims, W. B.; Solomon, E. I. J. Am. Chem. Soc. 1989, 111, 6106-6123 (e) Aasa, R.; Deinum, J.; Lerch, K.; Reinhammar B. Biochim. Biophys. Acta 1978, 535, 287-298.
24. Mixed-valence multicopper complexes usually are completely valence localized (class I), but in some instances spectroscopic evidence for delocalization of unpaired spin in a binuclear complex or dicopper protein active site. usually at elevated temperatures (>77 K), has been observed (class II behavior) For examples, see: (a) Dunaj-Jurco, M.; Ondrejovic, G.; Melnik, M. Coord. Chem. Rev. 1988, 83, 1-28 (b) Long, R. C.; Hendrickson, D. N. J. Am. Chem. Soc. 1983, 105, 1513-1521. (c) Gagné, R. R.; Koval, C. A.; Smith, T. J.; Cimolino, M. C J. Am. Chem. Soc. 1979, 101, 4571-4580. (d) Westmoreland, T. D.; Wilcox, D. E.; Baldwin, M. J.; Mims, W. B.; Solomon, E. I. J. Am. Chem. Soc. 1989, 111, 6106-6123 (e) Aasa, R.; Deinum, J.; Lerch, K.; Reinhammar B. Biochim. Biophys. Acta 1978, 535, 287-298.
25. Mixed-valence multicopper complexes usually are completely valence localized (class I), but in some instances spectroscopic evidence for delocalization of unpaired spin in a binuclear complex or dicopper protein active site. usually at elevated temperatures (>77 K), has been observed (class II behavior) For examples, see: (a) Dunaj-Jurco, M.; Ondrejovic, G.; Melnik, M. Coord. Chem. Rev. 1988, 83, 1-28 (b) Long, R. C.; Hendrickson, D. N. J. Am. Chem. Soc. 1983, 105, 1513-1521. (c) Gagné, R. R.; Koval, C. A.; Smith, T. J.; Cimolino, M. C J. Am. Chem. Soc. 1979, 101, 4571-4580. (d) Westmoreland, T. D.; Wilcox, D. E.; Baldwin, M. J.; Mims, W. B.; Solomon, E. I. J. Am. Chem. Soc. 1989, 111, 6106-6123 (e) Aasa, R.; Deinum, J.; Lerch, K.; Reinhammar B. Biochim. Biophys. Acta 1978, 535, 287-298.
26. Complete valence delocalization (class III behavior) mediated by a copper-copper bond has been reported: (a) Harding, C.; McKee, V.; Nelson, J J. Am. Chem. Soc. 1991, 113, 9584-9685. (b) Barr, M. E.; Smith, P. H.; Antholine, W.; Spencer. B. J. Chem Soc., Chem. Commun. 1993, 1649-1652. (c) Harding, C.; Nelson, J : Symons, M. C. R.; Wyatt, J. J. Chem. Soc., Chem. Commun. 1994, 2499-2500
27. Complete valence delocalization (class III behavior) mediated by a copper-copper bond has been reported: (a) Harding, C.; McKee, V.; Nelson, J J. Am. Chem. Soc. 1991, 113, 9584-9685. (b) Barr, M. E.; Smith, P. H.; Antholine, W.; Spencer. B. J. Chem Soc., Chem. Commun. 1993, 1649-1652. (c) Harding, C.; Nelson, J : Symons, M. C. R.; Wyatt, J. J. Chem. Soc., Chem. Commun. 1994, 2499-2500
28. Complete valence delocalization (class III behavior) mediated by a copper-copper bond has been reported: (a) Harding, C.; McKee, V.; Nelson, J J. Am. Chem. Soc. 1991, 113, 9584-9685. (b) Barr, M. E.; Smith, P. H.; Antholine, W.; Spencer. B. J. Chem Soc., Chem. Commun. 1993, 1649-1652. (c) Harding, C.; Nelson, J : Symons, M. C. R.; Wyatt, J. J. Chem. Soc., Chem. Commun. 1994, 2499-2500
29. (PrdacoS 1) See supporting information for synthetic details and characterization data for all new compounds, including 1. (a) Atkins, T. J.; Richman, J. E : Oettle, W. F. Organic Synthesis; John Wiley & Sons: New York, 1988; Collect Vol 6. pp 652-662. (b) Sessler, J L.; Sibert, J. W. Tetrahedron 1993, 49, 8727-8738.
30. (PrdacoS 1) See supporting information for synthetic details and characterization data for all new compounds, including 1. (a) Atkins, T. J.; Richman, J. E : Oettle, W. F. Organic Synthesis; John Wiley & Sons: New York, 1988; Collect Vol 6. pp 652-662. (b) Sessler, J L.; Sibert, J. W. Tetrahedron 1993, 49, 8727-8738.
31. Houser, R. P.; Halfen, J. A , Young, V G , Jr , Blackburn, N. J.; Tolman, W B. J. Am. Chem. Soc. 1995, 117, 10745-10746.
32. 2 using SHELXTL V5.0 converged with final Rl = 0.0444 and wR2 = 0.0867 for 5149 independent reflections with 1 > 2σ(1) and 393 parameters.
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37. ett = 1.7(1) μB.
38. max = 363 (1200), 480 (3000), 532 (3000), 808 (1600) nm.