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DOI: 10.1039/A900223E (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1999, 2177-2182

Enforcing geometrical constraints on metal complexes using biphenyl-based ligands: spontaneous reduction of copper(II) by sulfur-containing ligands

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Mitchell R. Malachowski, Mark Adams, Nadia Elia, Arnold L. Rheingold and Richard S. Kelly

Abstract

Two biphenyl-based N2S2 ligands, 2,2′-bis-(4-methylimidazol-5-yl)methylsulfanyl)biphenyl (N2S2-mim) and 2,2′-bis(2-pyridylmethylsulfanyl)biphenyl (N2S2-mpy), have been synthesized and their complexation with copper(II) precursors studied. In order to assess whether the biphenyl ring is influencing the geometry around the copper atom, the NS ligand 1-methyl-4-(2-pyridylmethylsulfanyl)benzene (NS-mpy) and its copper complexes were prepared. The N4 ligand 2,2′-bis-(2-pyridylmethylamino)biphenyl (N4-mpy) in which the sulfurs have been replaced by nitrogens also was prepared. Treatment of N4-mpy with copper(II) salts led to isolation of copper(II) complexes with the formula [Cu(N4-mpy)]X2 where X = ClO4 or BF4. These complexes were analysed by a combination of elemental analysis, IR spectroscopy, FAB MS and electrochemistry. Likewise, treatment of NS-mpy with copper(II) salts led to isolation of the copper(II) complexes [Cu(NS-mpy)2][ClO4]2 or [Cu(NS-mpy)2][BF4]2. In comparison to the results found for ligands N4-mpy and NS-mpy, treatment of N2S2-mim or N2S2-mpy with [Cu(H2O)6][ClO4]2 or [Cu(H2O)6][BF4]2 in MeOH led to spontaneous reduction to form the copper(I) complexes [Cu(N2S2-mim)]ClO4 [Cu(N2S2-mim)]BF4, [Cu(N2S2-mpy)]ClO4 and [Cu(N2S2-mpy)]BF4. The formulation of these complexes as copper(I) species was confirmed by analytical methods, and for [Cu(N2S2-mpy)]ClO4·MeCN by X-ray crystallography. The copper(I) ion is in a distorted tetrahedral environment ligated by two nitrogens and two thioethers from the ligand. Cyclic voltammetry shows [Cu(N2S2-mpy)]ClO4, [Cu(N4-mpy)][ClO4]2 and [Cu(NS-mpy)2][ClO4]2 undergo quasi-reversible one-electron processes with Eo′ is +0.77, +0.21 and +0.53 V vs. SCE.

References

  1. T. N. Sorrell, Tetrahedron, 1989, 45, 3 CrossRef.
  2. P. M. Colman, H. C. Freeman, J. M. Guss, M. Murata, V. A. Norris, J. A. M. Ramshaw and M. P. Venkatappa, Nature (London), 1978, 272, 319 CAS; E. I. Solomon, J. W. Hare, D. M. Dooley, J. H. Dawson, P. J. Stephens and H. B. Gray, J. Am. Chem. Soc., 1980, 102, 168 CrossRef CAS; J. S. Thompson, T. J. Marks and J. A. Ibers, J. Am. Chem. Soc., 1979, 101, 4180 CrossRef CAS.
  3. J. M. Guss and H. C. Freeman, J. Mol. Biol., 1983, 169, 521 CrossRef CAS; E. T. Adman, R. E. Stenkamp, L. C. Sieker and L. H. Jensen, J. Mol. Biol., 1978, 123, 35 CAS; G. E. Norris, B. F. Anderson and E. N. Baker, J. Am. Chem. Soc., 1986, 108, 2784 CrossRef CAS.
  4. E. Bouwman, W. L. Driessen and J. Reedijk, Coord. Chem. Rev., 1990, 104, 143 CrossRef CAS.
  5. L. Cassella, M. Gullotti, E. Suardi, M. Sisti, R. Pagliarin and P. Zanello, J. Chem. Soc., Dalton Trans., 1990, 2843 RSC.
  6. N. Kitajima, K. Fujisawa and Y. Moro-oka, J. Am. Chem. Soc., 1990, 112, 3210 CrossRef CAS.
  7. N. Kitajima, K. Fujisawa, M. Tanalka and Y. Moro-oka, J. Am. Chem. Soc., 1992, 114, 9232 CrossRef CAS.
  8. (a) F. Lions and K. V. Martin, J. Am. Chem. Soc., 1957, 79, 1273 CrossRef CAS; (b) H. Goodwin and F. Lions, J. Am. Chem. Soc., 1960, 82, 5013 CrossRef CAS; (c) T. P. Cheeseman, D. Hall and T. N. Waters, J. Chem. Soc. A, 1966, 1396 RSC.
  9. (a) S. Knapp, T. P. Keenan, X. Zhang, J. Liu, J. A. Potenza and H. J. Schugar, Inorg. Chem., 1990, 29, 2189 CrossRef CAS; (b) S. Knapp, T. P. Keenan, X. Zhang, R. Fikar, J. A. Potenza and H. J. Schugar, J. Am. Chem. Soc., 1990, 112, 3452 CrossRef CAS; (c) S. Knapp, T. P. Keenan, X. Zhang, R. Fikar, J. A. Potenza and H. J. Schugar, J. Am. Chem. Soc., 1987, 109, 1882 CrossRef CAS.
  10. E. Muller, C. Piguet, G. Bernardinelli and A. F. Williams, Inorg. Chem., 1988, 27, 849 CrossRef; E. Muller, G. Bernardinelli and J. Reedijk, Inorg. Chem., 1996, 35, 192 CrossRef.
  11. O. P. Anderson, J. Becher, H. Frydendahl, L. F. Taylor and H. Toftlund, J. Chem. Soc., Chem Commun., 1986, 699 RSC; H. Frydendahl, H. Toftlund, J. Becher, J. C. Dutton, K. S. Murray, L. F. Taylor, O. R. Anderson and R. T. Tiekink, Inorg. Chem., 1995, 34, 4476; H. Toftland, J. Becher, P. H. Olesen and J. Z. Pederson, Isr. J. Chem., 1985, 25, 56.
  12. P. Chautemps, G. Gellon, B. Morin, J. Pierre, C. Provent, S. M. Refaif, C. G. Beguin, E. Marqouki, G. Serratrice and E. Saint-Aman, Bull. Soc. Chim. Fr., 1994, 131, 434 CAS.
  13. M. Reglier, C. Jorand and B. Waegell, J. Chem. Soc., Chem. Commun., 1990, 1752 RSC.
  14. R. T. Jonas and T. D. P. Stack, J. Am. Chem. Soc., 1996, 118, 13097 CrossRef CAS; Y. Wang, J. L. Dubois, B. Hedman, K. O. Hodgson and T. D. P. Stack, Science, 1998, 279, 537 CrossRef CAS.
  15. M. R. Malachowski, B. T. Dorsey, M. J. Parker, M. E. Adams and R. S. Kelly, Polyhedron, 1998, 218, 1289 CrossRef CAS; M. R. Malachowski, M. G. Davidson, J. Carden, W. L. Driessen and J. Reedijk, Inorg. Chim. Acta, 1997, 257, 59 CrossRef CAS; M. R. Malachowski, B. T. Dorsey, J. G. Sackett, R. S. Kelly, A. L. Ferko and R. N. Hardin, Inorg. Chim. Acta, 1996, 249, 85 CrossRef CAS; M. R. Malachowski, H. B. Huynh, L. J. Tomlinson and R. S. Kelly, J. Chem. Soc., Dalton Trans, 1995, 31 RSC; M. R. Malachowski, L. J. Tomlinson, M. J. Parker and J. D. Davis, Tetrahedron Lett., 1992, 33, 1395 CrossRef CAS; M. R. Malachowski, M. G. Davidson and J. D. Davis, Inorg. Chim. Acta, 1992, 192, 157 CrossRef CAS.
  16. T. N. Sorrell and E. H. Cheesman, Synth. Commun., 1981, 11, 909 CAS.
  17. L. R. Melby, J. Am. Chem. Soc., 1975, 97, 4044 CrossRef CAS.
  18. A. I. Vogel, Quantitative Inorganic Analysis, Longmans, London, 1961 Search PubMed.
  19. G. M. Sheldrick, SHELXTL 5.03, Bruker AXS, Madison, WI, 1988.
  20. E. Bouwman and W. L. Driessen, Synth. Commun., 1988, 18, 1581 CAS.
  21. K. K. Nanda, A. W. Addison, R. J. Butcher, M. R. McDevitt, T. N. Rao and E. Sinn, Inorg. Chem., 1997, 36, 134 CrossRef CAS.
  22. S. Kitagawa, M. Munakata and A. Higashi, Inorg. Chim. Acta, 1984, 84, 79 CrossRef CAS.
  23. T. Sakurai, M. Kimura and A. Nakahara, Bull. Chem. Soc. Jpn., 1981, 54, 2976 CAS.
  24. J. M. Latour, D. Limosin and P. Rey, J. Chem. Soc., Chem. Commun., 1985, 464 RSC.
  25. M. M. Olmstead, W. K. Musker and R. M. Kessler, Inorg. Chem., 1981, 20, 151 CrossRef CAS.
  26. A. Benzekri, C. Cartier, J. M. Latour, D. Limosin, P. Rey and M. Verdaguer, Inorg. Chim. Acta, 1996, 252, 413 CrossRef CAS.
  27. P. L. Verheijdt, J. G. Haasnoot and J. Reedijk, Inorg. Chim. Acta, 1983, 76, L43 CrossRef CAS; P. J. M. W. L. Birker, J. Helder, G. Henkel, B. Krebs and J. Reedijk, Inorg. Chem., 1982, 21, 357 CrossRef CAS; M. J. Schilstra, P. J. M. W. L. Birker, G. Verschoor and J. Reedijk, Inorg. Chem., 1982, 21, 2637 CrossRef CAS.
  28. N. Wei, N. N. Murthy, Z. Tyeklar and K. D. Karlin, Inorg. Chem,, 1994, 33, 1177 CrossRef CAS.
  29. A. G. Orpen, L. Brammer, F. H. Allen, O. Kennard, D. G. Watson and R. Taylor, J. Chem. Soc., Dalton Trans., 1989, S1 RSC.
  30. H. B. Gray, C. L. Cycle, D. M. Dooley, P. J. Grunthaner, J. W. Hare, R. A. Holwerda, J. V. McArdle, D. R. McMillan, J. Rawlings, R. C. Rosenberg, N. Sailasuta, E. I. Soloman, P. J. Stephens, S. Wherland and J. A. Wurzbach, In Bioinorganic Chemistry II, American Chemical Society, Washington, DC, 1977, p. 145 Search PubMed.
  31. J. R. Dorfman, R. D. Bereman and M. H. Whangbo, in Copper Coordination Chemistry: Biochemical and Inorganic Perspectives, eds. K. D. Karlin and J. Zubieta, Adenine, Guilderland, NY, 1983, p. 75 Search PubMed.
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