View PDF Version
 
DOI: 10.1039/A806657D (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1998, 3791-3800

Co-ordination chemistry of bis(ferrocenylcarbaldimine) Schiff bases

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

Peiyi Li, Ian J. Scowen, John E. Davies and Malcolm A. Halcrow

Abstract

The complex chemistries of 1,2-bis(ferrocen-1-ylmethyleneamino)ethane (L1), 1,2-bis(ferrocen-1-ylmethyleneamino)benzene (L2) and its 4-methyl (L3), 4-chloro (L4) and 4-nitro (L5) derivatives have been reexamined. Complexation of L1 by ZnCl2 afforded [ZnCl2(L1)], whose single crystal structure reveals a distorted tetrahedral zinc(II) centre with Zn[hair space][hair space]· · ·[hair space][hair space]Fe 4.730(2) and 4.803(2) Å. The complexes [ZnCl2(L)] (L = L2–L5), [ZnBr2(L)] (L = L2–L5) and [CoBr2(L3)] are accessible by MX2-templated condensation of 2 equivalents of ferrocenecarbaldehyde (fcCHO) with the appropriate 1,2-diaminobenzene. Treatment of [Cu(NCMe)4]X (X– = BF4– or PF6–) with L1, or fcCHO and the corresponding 1,2-diaminobenzene, yielded [Cu(L)2]X (L = L1–L3). The single crystal structure of [Cu(L3)2]PF6·1.7CH2Cl2 shows a tetrahedral copper(I) centre, the chelate ligands being substantially distorted from planarity. Compounds [ZnCl2(L)], [ZnBr2(L)] (L = L2–L5) and [CoBr2(L3)[hair space]] exhibit weak electronic communication between the two ferrocenyl centres, showing by cyclic voltammetry two chemically reversible FeII–FeIII oxidations separated by 50–60 mV in CH2Cl2–0.5 M NBun4PF6 at 293 K; [ZnCl2(L1)] and [Cu(L)2]X (L = L1–L3) exhibit a single FeII–FeIII couple under these conditions. Attempted template syntheses of L2–L5 employing other MX2 (M = Mn, Co, Ni or Cu; X– = Cl–, Br–, NO3–, BF4– or ClO4–) salts yielded primarily 2-ferrocenylbenzimidazole intramolecular cyclisation derivatives; the crystal structure of one such product was determined.

References

  1. A. Togni and T. Hayashi(Editors), Ferrocenes. Homogeneous Catalysis. Organic Synthesis. Materials Science, VCH, Weinheim, 1995 Search PubMed.
  2. P. D. Beer, Adv. Inorg. Chem., 1992, 39, 79 CAS; P. D. Beer and D. K. Smith, Prog. Inorg. Chem., 1997, 46, 1 CAS.
  3. J. S. Miller and A. J. Epstein, Angew. Chem., Int. Ed. Engl., 1994, 33, 385 CrossRef.
  4. N. J. Long, Angew. Chem., Int. Ed. Engl., 1995, 34, 21 CrossRef CAS; S. R. Marder, in Inorganic Materials, eds. D. W. Bruce and D. O'Hare, Wiley, Chichester, 1996, ch. 3, pp. 121–169 Search PubMed.
  5. A. Houlton, N. Jasim, R. M. G. Roberts, J. Silver, D. Cunningham, P. McArdle and T. Higgins, J. Chem. Soc., Dalton Trans., 1992, 2235 RSC; A. Houlton, J. R. Miller, J. Silver, N. Jasim, M. J. Ahmet, T. L. Axon, D. Bloor and G. H. Gross, Inorg. Chim. Acta, 1993, 205, 67 CrossRef CAS; J. Silver, J. R. Miller, A. Houlton and M. J. Ahmet, J. Chem. Soc., Dalton Trans., 1994, 3355 RSC; R. Bosque, C. Lopez, J. Sales, X. Solans and M. Font-Bardia, J. Chem. Soc., Dalton Trans., 1994, 735 RSC; Y. J. Wu, S. Q. Huo and Y. Zhu, J. Organomet. Chem., 1995, 485, 161 CrossRef CAS; S. Q. Huo and Y. J. Wu, J. Organomet. Chem., 1995, 490, 243 CrossRef CAS; C. Lopez, R. Bosque, X. Solans and M. Font-Bardia, New J. Chem., 1996, 20, 1285 Search PubMed.
  6. C. Lopez, J. Sales, X. Solans and J. Reedijk, J. Chem. Soc., Dalton Trans., 1992, 2321 RSC; J. Blanco, E. Gayoso, J. M. Vila, M. Gayoso, C. Maichle-Mossmer and J. Strahle, Z. Naturforsch., Teil B, 1993, 48, 906 CAS; S. Q. Huo, Y. J. Wu, Y. Zhu and L. Yang, J. Organomet. Chem., 1994, 470, 17 CrossRef CAS; Y. J. Wu, S. Q. Huo, Y. Zhu and L. Yang, J. Organomet. Chem., 1994, 481, 235 CrossRef CAS; R. Bosque, C. Lopez, J. Sales and X. Solans, J. Organomet. Chem., 1994, 483, 61 CrossRef CAS; C. Lopez, R. Bosque, X. Solans, M. Font-Bardia, D. Tramuns, G. Fern and J. Silver, J. Chem. Soc., Dalton Trans., 1994, 3039 RSC; Y. Yoshida, K. Onitsuka and K. Sonogashira, J. Organomet. Chem., 1996, 511, 47 CrossRef.
  7. M. J. L. Tendero, A. Benito, J. M. Lloris, R. Martínez-Mañez, J. Soto, J. Payá, A. J. Edwards and P. R. Raithby, Inorg. Chim. Acta, 1996, 247, 139 CrossRef CAS; M. J. L. Tendero, A. Benito, R. Martínez-Mañez, J. Soto, J. Payá, A. J. Edwards and P. R. Raithby, J. Chem. Soc., Dalt on Trans., 1996, 343 RSC.
  8. E. W. Nause, M. G. Meirim and N. F. Blom, Organometallics, 1988, 7, 2562 CrossRef CAS.
  9. A. Benito, J. Cano, R. Martínez-Máñez, J. Soto, J. Payá, F. Lloret, M. Julve, J. Faus and M. D. Marcos, Inorg. Chem., 1993, 32, 1197 CrossRef CAS.
  10. A. Benito, R. Martínez-Máñez, J. Payá, J. Soto, M. J. L. Tendero and E. Sinn, J. Organomet. Chem., 1995, 503, 259 CrossRef CAS.
  11. J. Cano, A. Benito, R. Martínez-Máñez, J. Soto, J. Payá, F. Lloret, M. Julve, M. D. Marcos and E. Sinn, Inorg. Chim. Acta, 1995, 231, 45 CrossRef CAS.
  12. R. J. Less, J. L. M. Wicks, N. P. Chatterton, M. J. Dewey, N. L. Cromhout, M. A. Halcrow and J. E. Davies, J. Chem. Soc., Dalton Trans., 1996, 4055 RSC.
  13. C. Li, X. Peng and X.-Z. You, Synth. React. Org. Metal-Org. Chem., 1990, 20, 1231 Search PubMed; C. Li, X.-Z. You, X. Peng, C.-Y. Zhao and H.-Y. Wu, Transition Met. Chem., 1995, 20, 300 CAS.
  14. D. Freiesleben, K. Polborn, C. Robl, K. Sünkel and W. Beck, Can. J. Chem., 1995, 73, 1164 CAS.
  15. T. Kawamoto and Y. Kushi, J. Chem. Soc., Dalton Trans., 1992, 3137 RSC; I. Nagasawa, T. Kawamoto, H. Kuma and Y. Kushi, Bull. Chem. Soc. Jpn., 1998, 71, 1337 CAS.
  16. P. J. Palmer, R. B. Trigg and J. V. Warrington, J. Med. Chem., 1971, 14, 248 CrossRef CAS.
  17. R. H. Holm, A. Chakravorty and G. O. Dudek, J. Am. Chem. Soc., 1964, 86, 379 CrossRef CAS.
  18. A. G. Orpen, L. Brammer, F. H. Allen, O. Kennard, D. G. Watson and R. Taylor, J. Chem. Soc., Dalton Trans., 1989, S1 RSC.
  19. E. Müller, C. Piguet, G. Bernardinelli and A. F. Williams, Inorg. Chem., 1988, 27, 849 CrossRef; D. A. Bardwell, A. M. W. Cargill Thompson, J. C. Jeffrey, E. E. M. Tilley and M. D. Ward, J. Chem. Soc., Dalton Trans., 1995, 835 RSC; S. M. Scott, K. C. Gordon and A. K. Burrell, Inorg. Chem., 1996, 35, 2452 CrossRef CAS.
  20. M. A. Halcrow, N. L. Cromhout and P. R. Raithby, Polyhedron, 1997, 16, 4257 CrossRef CAS and refs. therein.
  21. Y. S. Sohn, D. N. Hendrickson and H. B. Gray, J. Am. Chem. Soc., 1971, 93, 3603 CrossRef.
  22. S. Toma, A. Gáplovsky, M. Hudecek and Z. Langfelderová, Monatsh. Chem., 1985, 116, 357 CAS; M. M. Bhadbhade, A. Das, J. C. Jeffrey, J. A. McCleverty, J. A. Navas Badiola and M. D. Ward, J. Chem. Soc., Dalton Trans., 1995, 2769 RSC.
  23. C. Reichardt, Angew. Chem., Int. Ed. Engl., 1965, 4, 29 CrossRef.
  24. A. B. P. Lever, Inorganic Electronic Spectroscopy, 2nd edn., Elsevier, Amsterdam, 1984 Search PubMed.
  25. D. R. Scott and R. S. Becker, J. Chem. Phys., 1961, 35, 516 CrossRef CAS.
  26. S. Kitagawa and M. Munakata, Inorg. Chem., 1981, 20, 2261 CrossRef CAS; M. A. Masood and P. S. Zacharias, J. Chem. Soc., Dalton Trans., 1991, 111 RSC.
  27. Z. Yu, Y. Zhou, W. Yang, Y. Tian, C.-Y. Duan, R. Liu and X. You, Chem. Lett., 1996, 957 CAS.
  28. M. D. Ward, Chem. Soc. Rev., 1995, 24, 121 RSC.
  29. P. Federlin, J.-M. Kern, A. Rastegar, C. Dietrich-Buchecker, P. A. Marnot and J.-P. Sauvage, New J. Chem., 1980, 14, 9 Search PubMed.
  30. E. C. Constable, Metals and Ligand Reactivity, 2nd edn., VCH, Weinheim, 1996 Search PubMed.
  31. G. M. Sheldrick, SHELXTL PLUS, PC version, Siemens Analytical X-Ray Instruments Inc., Madison, WI, 1990.
  32. G. M. Sheldrick, SHELXL 97, University of Göttingen, 1997.
  33. S. Parkin, B. Moezzi and H. Hope, J. Appl. Crystallogr., 1995, 28, 53 CrossRef CAS.
  34. N. Walker and D. Stuart, Acta Crystallogr., Sect. A, 1983, 39, 158 CrossRef.
Click here to see how this site uses Cookies. View our privacy policy here.