Nickel complexes with tris(2-aminoethyl)amine (tren): [Ni3(tren)4(H2O)2][Cr(ox)3]2·6H2O (ox = oxalate), {[Ni2(tren)3][ClO4]4·H2O}n, and [Ni2(tren)2(aepd)][ClO4]4·2H2O (aepd = N-(2-aminoethyl)pyrrolidine-3,4-diamine). Synthesis, structure and magnetism[hair space]

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

Vanessa M. Masters, Paul V. Bernhardt, Lawrence R. Gahan, Boujemaa Moubaraki, Keith S. Murray and Kevin J. Berry


Abstract

Reaction of K3[Cr(ox)3] (ox = oxalate) with nickel(II) and tris(2-aminoethyl)amine (tren) in aqueous solution resulted in isolation of the bimetallic assembly [Ni3(tren)4(H2O)2][Cr(ox)3]2·6H2O. The polymeric complex {[Ni2(tren)3][ClO4]4·H2O}n has been prepared by reaction of nickel(II) perchlorate and tren in aqueous solution. From the same reaction mixture the complex [Ni2(tren)2(aepd)][ClO4]4·2H2O (aepd = N-(2-aminoethyl)pyrrolidine-3,4-diamine), in which a bridging tren ligand contains a carbon–carbon bond between two arms forming a substituted pyrrolidine, has been isolated. The complexes have been characterized by X-ray crystallography. The magnetic susceptibility (300–4.2 K) and magnetization data (2, 4 K, H = 0–5 T) for {[Ni2(tren)3][ClO4]4·H2O}n (300 K , 4.23 µB) exhibit evidence of weak antiferromagnetic coupling and zero field splitting (2J = –1.8 cm–1; |D| = 2 cm–1) at low temperature. For [Ni3(tren)4(H2O)2][Cr(ox)3]2·6H2O the susceptibility data at 300 K are indicative of uncoupled nickel(II) and chromium(III) sites with zero-field splitting and intramolecular antiferromagnetic coupling predicted at low temperature.


References

  1. K. S. Murray, G. D. Fallon, D. C. R. Hockless, K. D. Lu, B. Moubaraki and K. Van Langenberg, ACS Symp. Ser., 1996, 644, 201 CAS.
  2. M. C. Morón, F. Palacio, J. Pons, J. Casabó, X. Solans, K. E. Merabet, D. Huang, X. Shi, B. K. Teo and R. L. Carlin, Inorg. Chem., 1994, 33, 746 CrossRef CAS.
  3. R. L. Carlin, Comments Inorg. Chem., 1991, 11, 215 CAS.
  4. S. Decurtins, H. W. Schmalle, P. Schneuwly and H. R. Oswald, Inorg. Chem., 1993, 32, 1888 CrossRef CAS.
  5. V. A. Grillo, L. R. Gahan, G. R. Hanson and T. W. Hambley, Polyhedron, 1996, 15, 559 CrossRef CAS.
  6. M. C. Morón, A. Le Bail and J. Pons, J. Solid State Chem., 1990, 88, 498 CAS.
  7. Y. Pei, Y. Journaux and O. Kahn, Inorg. Chem., 1989, 28, 100 CrossRef CAS.
  8. T. Mallah, C. Auberger, M. Verdaguer and P. Veillet, J. Chem. Soc., Chem. Commun., 1995, 61 RSC.
  9. V. Gadet, T. Mallah, I. Castro and M. Verdaguer, J. Am. Chem. Soc., 1992, 114, 9213 CrossRef CAS.
  10. A. P. Ginsberg, Inorg. Chim. Acta Rev., 1971, 5, 45 Search PubMed.
  11. S. R. Hall, H. D. Flack and J. M. Stewart(Editors), The XTAL3.2 User's Manual, Universities of Western Australia, Geneva and Maryland, 1992 Search PubMed.
  12. G. M. Sheldrick, Acta Crystallogr., Sect. A, 1990, 46, 467 CrossRef.
  13. G. M. Sheldrick, SHELXL 93, A program for crystal structure determination, University of Göttingen, 1993.
  14. A. L. Spek, PLATON, A Thermal ellipsoid plotting program, University of Utrecht, 1994.
  15. A. Marzotto, D. A. Clemente and G. Valle, Acta Crystallogr., Sect. C, 1993, 49, 1252 CrossRef.
  16. D. Taylor, Aust. J. Chem., 1978, 31, 1455 CAS.
  17. F. G. Mann, J. Chem. Soc., 1929, 409 RSC.
  18. F. G. Mann and W. J. Pope, J. Chem. Soc., 1926, 482 RSC.
  19. C. K. Jørgensen, Acta Chem. Scand., 1956, 10, 887 CAS.
  20. G. J. Colpas, M. Kumar, R. O. Day and M. J. Maroney, Inorg. Chem., 1990, 29, 4779 CrossRef CAS.
  21. M. Shalah El Fallah, E. Rentschler, A. Caneschi, R. Sessoli and D. Gatteschi, Angew. Chem., Int. Ed. Engl., 1996, 35, 1947 CrossRef CAS.
  22. R. D. Willett, Acta Crystallogr., Sect. C, 1987, 43, 1494 CrossRef.
  23. M. L. Calatayud, I. Castro, J. Sletten, J. Cano, F. Lloret, J. Faus, M. Julve, G. Seitz and K. Mann, Inorg. Chem., 1996, 35, 2858 CrossRef.
  24. The lel and ob nomenclature is described in Inorg. Chem., 1970, 9, 1 Search PubMed.
  25. M. Ohba, N. Fukita and H. Ōkawa, J. Chem. Soc., Dalton Trans., 1997, 1733 RSC.
  26. H. L. Shyu, H. H. Wei and Y. Wang, Inorg. Chim. Acta, 1997, 258, 81 CrossRef CAS.
  27. A. Meyer, A. Gleizes, J.-J. Girerd, M. Verdaguer and O. Kahn, Inorg. Chem., 1982, 21, 1729 CrossRef CAS.
  28. O. Kahn, Molecular Magnetism, VCH, New York, 1993, p. 257 Search PubMed.
  29. K. S. Murray, Adv. Inorg. Chem., 1995, 43, 261 CrossRef CAS.
  30. J. Glerup, P. A. Goodson, D. J. Hodgson and K. Michelson, Inorg. Chem., 1995, 34, 6255 CrossRef CAS.
  31. Y. Journaux, J. Sletten and O. Kahn, Inorg. Chem., 1986, 25, 439 CrossRef CAS.
  32. P. Chaudhuri, M. Winter, B. P. C. Della Vdova, E. Bill, A. Trautwein, S. Gehring, P. Fleischhauer, B. Nuber and J. Weiss, Inorg. Chem., 1991, 30, 2148 CrossRef CAS.
  33. R. Ruiz, M. Julve, J. Faus, F. Lloret, M. C. Muñoz, Y. Journaux and C. Bois, Inorg. Chem., 1997, 36, 3434 CrossRef CAS.
  34. L. N. Mulay, Magnetic Susceptibility, Interscience Publishers, New York, 1963, p. 1751 Search PubMed.
  35. L. R. Gahan and V. M. Masters, unpublished work.
Click here to see how this site uses Cookies. View our privacy policy here.