View PDF Version
 
DOI: 10.1039/A902793I (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1999, 2371-2384

Generation of substrate-binding sites by electrochemical reduction of cis-[Fe2(cp)2(µ-SMe)2(MeCN)(L)]2+ (L = CO or MeCN). Reactivity of the sites toward CO and tBuNC. Crystal structure of [Fe2(cp)2(µ-SMe)2(CO)(MeCN)][BF4]2·CH2Cl2

(Note: The full text of this document is currently only available in the PDF Version )

Pascale Madec, Kenneth W. Muir, François Y. Pétillon, René Rumin, Yannick Scaon, Philippe Schollhammer and Jean Talarmin

Abstract

Iron complexes with the {Fe2(cp)2(µ-SMe)2} core have been synthesized and their electrochemistry investigated. Electrochemical reduction of the acetonitrile-substituted complexes cis-[Fe2(cp)2(µ-SMe)2(MeCN)2]2+ and cis-[Fe2(cp)2(µ-SMe)2(CO)(MeCN)]2+ labilizes the MeCN ligand(s) and generates vacant sites at which CO and isocyanide substrates can bind. The mechanism of the electrochemical reduction of both complexes has been investigated in the presence of these substrates. A single-crystal X-ray analysis established that cis-[Fe2(cp)2(µ-SMe)2(CO)(MeCN)][BF4]2 contains an unusual dication in which different ligands (CO, MeCN) occupy corresponding sites in the co-ordination polyhedra of the two iron centres of the Fe2(µ-S)2 ring. Aspects of the reactivity and electrochemistry of complexes with Fe2(µ-SMe)2 and Mo2(µ-SR)2 cores are compared.

References

  1. R. H. Holm, P. Kennepohl and E. I. Solomon, Chem. Rev., 1996, 96, 2239 CrossRef CAS.
  2. H. Ogino, S. Inomata and H. Tobita, Chem. Rev., 1998, 98, 2093 CrossRef CAS.
  3. R. B. King and M. B. Bisnette, Inorg. Chem., 1965, 4, 482 CrossRef CAS.
  4. (a) B. I. Kolobkov, S. E. Nefedov, I. L. Eremenko, A. A. Pasynskii, A. I. Yanovskii and Yu. T. Struchkov, Zh. Neorg. Khim., 1992, 37, 328 Search PubMed; (b) G. Ferguson, C. Hannaway and K. M. S. Islam, Chem. Commun., 1968, 1165 RSC.
  5. N. G. Connelly and L. F. Dahl, J. Am. Chem. Soc., 1970, 92, 7472 CrossRef.
  6. M. Chase, H. A. O. Hill, C. E. Johnson and R. Richards, Chem. Commun., 1970, 1376 RSC.
  7. J. A. de Beer, R. J. Haines, R. Greatrex and J. A. van Wyk, J. Chem. Soc., Dalton Trans., 1973, 2341 RSC.
  8. J. A. de Beer, R. J. Haines and R. Greatrex, J. Organomet. Chem., 1975, 85, 89 CrossRef.
  9. P. D. Frisch, M. K. Lloyd, J. A. McCleverty and D. Seddon, J. Chem. Soc., Dalton Trans., 1973, 2268 RSC.
  10. D. D. Watkins and T. A. George, J. Organomet. Chem., 1975, 102, 71 CrossRef CAS.
  11. R. B. English, Acta Crystallogr., Sect. C, 1984, 40, 1567 CrossRef.
  12. W. Gaete, J. Ros, R. Yanez, X. Solans and M. Font-Altaba, J. Organomet. Chem., 1986, 316, 169 CrossRef CAS.
  13. A. A. Pasynskii, I. L. Eremenko, M. A. Porai-Koshits, S. B. Katser, A. S. Antsyshkina, A. S. Katugin, B. Orazsakhatov, O. Y. Okhlobystin and V. I. Privalov, Metalloorg. Khim., 1990, 3, 454 Search PubMed.
  14. M. T. Toshev, Kh. B. Dustov, A. I. Nekhaev, G. G. Aleksandrov, S. D. Alekseeva and B. I. Kolobkov, Koord. Khim., 1991, 17, 930 Search PubMed.
  15. R. Büchner, J. S. Field and R. J. Haines, J. Chem. Soc., Dalton Trans., 1996, 3533; 1997, 2403 Search PubMed.
  16. G. J. Kubas and P. J. Vergamini, Inorg. Chem., 1981, 20, 2667 CrossRef CAS.
  17. P. J. Vergamini and G. J. Kubas, Prog. Inorg. Chem., 1976, 21, 261 CAS.
  18. S. Dev, Y. Mizobe and M. Hidai, Inorg. Chem., 1990, 29, 4797 CrossRef CAS.
  19. U. Koelle, C. Rietmann and U. Englert, J. Organomet. Chem., 1992, 423, C20 CrossRef.
  20. A. Hörnig, C. Rietmann, U. Englert, T. Wagner and U. Kölle, Chem. Ber., 1993, 126, 2609 CrossRef.
  21. M. Hidai, Y. Mizobe and H. Matsuzaka, J. Organomet. Chem., 1994, 473, 1 CrossRef CAS and refs. therein.
  22. H. Matsuzaka, Y. Takagi and M. Hidai, Organometallics, 1994, 13, 13 CrossRef CAS.
  23. U. Koelle, C. Rietmann, J. Tjoe, T. Wagner and U. Englert, Organometallics, 1995, 14, 703 CrossRef.
  24. S. Kuwata, Y. Mizobe and M. Hidai, Inorg. Chem., 1994, 33, 3619 CrossRef CAS.
  25. F. Y. Pétillon, P. Schollhammer, J. Talarmin and K. W. Muir, Coord. Chem. Rev., 1998, 178–180, 203 CrossRef CAS.
  26. P. Schollhammer, F. Y. Pétillon, S. Poder-Guillou, J. Y. Saillard, J. Talarmin and K. W. Muir, Chem. Commun., 1996, 2633 RSC; P. Schollhammer, E. Guénin, F. Y. Pétillon, J. Talarmin, K. W. Muir and D. S. Yufit, Organometallics, 1998, 17, 1922 CrossRef CAS.
  27. J. F. Capon, P. Schollhammer, F. Y. Pétillon, J. Talarmin and K. W. Muir, unpublished work.
  28. (a) M. Guéguen, F. Y. Pétillon and J. Talarmin, Organometallics, 1989, 8, 148 CrossRef CAS; (b) F. Y. Pétillon, S. Poder-Guillou, P. Schollhammer and J. Talarmin, New J. Chem., 1997, 21, 477 Search PubMed.
  29. F. Gloaguen, C. Le Floch, F. Y. Pétillon, J. Talarmin, M. El Khalifa and J. Y. Saillard, Organometallics, 1991, 10, 2004 CrossRef CAS.
  30. S. D. Killops and S. A. R. Knox, J. Chem. Soc., Dalton Trans., 1978, 1260 RSC.
  31. H. S. Gutowski and C. H. Holm, J. Chem. Phys., 1956, 25, 1228 CrossRef CAS.
  32. H. Shanan-Atidi and K. H. Bar-Eli, J. Chem. Phys., 1970, 74, 961 CAS.
  33. J. Sandström, in Dynamic NMR Spectroscopy, Academic Press, London, New York, 1982 Search PubMed.
  34. M. Guéguen, J. E. Guerchais, F. Y. Pétillon and J. Talarmin, J. Chem. Soc., Chem. Commun., 1987, 557 RSC.
  35. A. J. Bard and L. R. Faulkner, Electrochemical Methods. Fundamentals and Applications, Wiley, New York, 1980, ch. 11, pp. 429–485 Search PubMed; E. R. Brown and R. F. Large, in Techniques of Chemistry, ed. A. Weissberger, New York, Wiley, 1971, vol. 1, part IIA, ch. 6, pp. 423–530 Search PubMed.
  36. R. S. Nicholson and I. Shain, Anal. Chem., 1964, 36, 706 CrossRef CAS.
  37. R. S. Nicholson, Anal. Chem., 1966, 38, 1406 CrossRef CAS.
  38. R. Hill, B. A. Kelly, F. G. Kennedy, S. A. R. Knox and P. Woodward, J. Chem. Soc., Chem. Commun., 1977, 434 RSC.
  39. N. G. Connelly, G. A. Johnson, B. A. Kelly and P. Woodward, J. Chem. Soc., Chem. Commun., 1977, 436 RSC.
  40. A. Takahashi, Y. Mizobe, H. Matsuzaka, S. Dev and M. Hidai, J. Organomet. Chem., 1993, 456, 243 CrossRef CAS.
  41. W. E. Geiger, P. H. Rieger, B. Tulyathan and M. D. Raush, J. Am. Chem. Soc., 1984, 106, 7000 CrossRef CAS.
  42. M. L. Abasq, D. L. Hughes, F. Y. Pétillon, R. Pichon, C. J. Pickett and J. Talarmin, J. Chem. Soc., Dalton Trans., 1997, 2279 RSC.
  43. I. D. Benson, S. D. Killops, S. A. R. Knox and A. J. Welch, J. Chem. Soc., Chem. Commun., 1980, 1137 RSC.
  44. R. D. Adams, D. F. Chodosh and E. Faraci, Cryst. Struct. Comm., 1978, 7, 145 Search PubMed.
  45. J. Courtot-Coupez, M. Guéguen, J. E. Guerchais, F. Y. Pétillon, J. Talarmin and R. Mercier, J. Organomet. Chem., 1986, 312, 81 CrossRef CAS.
  46. M. El Khalifa, F. Y. Pétillon, J. Y. Saillard and J. Talarmin, Inorg. Chem., 1989, 28, 3849 CrossRef.
  47. S. Shaik, R. Hoffmann, C. R. Fisel and R. H. Summerville, J. Am. Chem. Soc., 1980, 102, 4555 CrossRef.
  48. W. E. Geiger, Prog. Inorg. Chem., 1985, 33, 275 CAS.
  49. D. H. Evans and K. M. O'Connell, in Electroanalytical Chemistry, ed. A. J. Bard, Marcel Dekker, New York, 1986, vol. 14, p. 113 Search PubMed.
  50. T. Gennett, W. E. Geiger, B. Willett and F. C. Anson, J. Electroanal. Chem. Interfacial Electrochem., 1987, 222, 151 CrossRef CAS.
  51. N. G. Connelly and L. F. Dahl, J. Am. Chem. Soc., 1970, 92, 7470 CrossRef.
  52. M. El Khalifa, M. Guéguen, R. Mercier, F. Y. Pétillon, J. Y. Saillard and J. Talarmin, Organometallics, 1989, 8, 140 CrossRef CAS.
  53. J. F. Capon, R. Kergoat, N. Le Berre-Cosquer, S. Péron, J. Y. Saillard and J. Talarmin, Organometallics, 1997, 16, 4645 CrossRef CAS.
  54. R. Hoffmann and W. N. Lipscomb, J. Chem. Phys., 1962, 36, 2179 CrossRef CAS; R. Hoffmann, J. Chem. Phys., 1963, 39, 1397 CrossRef CAS.
  55. J. M. Ammeter, H. B. Bürgi, J. C. Thibeault and R. Hoffmann, J. Am. Chem. Soc., 1978, 100, 3686 CrossRef CAS.
  56. S. Alvarez, Tables of Parameters for Extended Hückel Calculations, Departemento de Quimica Inorganica, University of Barcelona, 1989.
  57. C. Mealli and . Proserpio, J. Chem. Educ., 1990, 67, 399 CrossRef CAS.
  58. G. M. Sheldrick, SADABS, A program for empirical absorption correction, University of Göttingen, 1997.
  59. G. M. Sheldrick, SHELXL 97, A program for the reWnement of crystal structures, University of Göttingen, 1997.
  60. L. J. Farrugia, WINGX, A program system for X-ray analysis, University of Glasgow, 1997.
Click here to see how this site uses Cookies. View our privacy policy here.