View PDF Version
 
DOI: 10.1039/A802300J (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1998, 2185-2190

Macrocyclic selenoether complexes of nickel(II). Synthesis and properties of [NiX2([16]aneSe4)] ([16]aneSe4 = 1,5,9,13-tetraselenacyclohexadecane, X = Cl, Br or I) and [NiX2(MeSeCH2CH2SeMe)2][hair space]*

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

Maxwell K. Davies, William Levason and Gillian Reid

Abstract

Reaction of NiX2 (X = Cl, Br or I) with [16]aneSe4 (1,5,9,13-tetraselenacyclohexadecane) under anhydrous conditions in n-butanol yielded trans-[NiX2([16]aneSe4)]. Similar reactions using MeSeCH2CH2SeMe produced trans-[NiX2(MeSeCH2CH2SeMe)2]. The complexes have been characterised by IR and UV/VIS spectroscopy and magnetic measurements. The crystal structure of [NiCl2(MeSeCH2CH2SeMe)2] showed an octahedral nickel centre co-ordinated to trans chlorines [2.370(2)–2.376(2) Å] with the diselenoethers present as chelating ligands in the DL conformation [2.522(1)–2.5623(8) Å]. Structural data on the very poorly soluble [16]aneSe4 complexes were obtained via nickel K-edge EXAFS (extended X-ray absorption fine structure), and the results compared with related complexes. A ligand field analysis of the UV/VIS spectra of [NiX2([16]aneSe4)] and of the tetrathioether analogues [NiX2([16]aneS4)] ([16]aneS4 = 1,5,9,13-tetrathiacyclohexadecane) showed that the ligand fields produced by 16-membered ring macrocycles [Dq(xy)] lie in the order N4 > S4 > Se4, with MeSeCH2CH2SeMe affording a stronger field that [16]aneSe4 due to the smaller chelate ring size.

References

  1. S. G. Murray and F. R. Hartley, Chem. Rev., 1981, 81, 365 CrossRef CAS.
  2. E. G. Hope and W. Levason, Coord. Chem. Rev., 1993, 122, 109 CrossRef CAS.
  3. A. J. Blake and M. Schröder, Adv. Inorg. Chem., 1990, 35, 1 CAS; S. R. Cooper and S. C. Rawle, Struct. Bonding (Berlin), 1990, 72, 1 CAS.
  4. R. J. Batchelor, F. W. B. Einstein, I. D. Gray, J.-H. Gu, B. D. Johnson and B. M. Pinto, J. Am. Chem. Soc., 1989, 111, 6582 CrossRef CAS.
  5. N. R. Champness, P. F. Kelly, W. Levason, G. Reid, A. M. Z. Slawin and D. J. Williams, Inorg. Chem., 1995, 34, 651 CrossRef CAS.
  6. W. Levason, J. J. Quirk, G. Reid and C. S. Frampton, Inorg. Chem., 1994, 33, 6120 CrossRef CAS.
  7. W. Levason, J. J. Quirk and G. Reid, J. Chem. Soc., Dalton Trans., 1996, 3713 RSC.
  8. W. Levason, J. J. Quirk, G. Reid and S. M. Smith, J. Chem. Soc., Dalton Trans., 1997, 3719 RSC.
  9. R. J. Batchelor, F. W. B. Einstein, I. D. Gray, J.-H. Gu, B. M. Pinto and X. M. Zhou, J. Am. Chem. Soc., 1990, 112, 3706 CrossRef CAS; J. Organomet. Chem., 1991, 411, 147 Search PubMed.
  10. W. Levason, G. Reid and S. M. Smith, Polyhedron, 1997, 16, 4253 CrossRef CAS.
  11. A. J. Blake, M. A. Halcrow and M. Schröder, J. Chem. Soc., Dalton Trans., 1994, 1463 RSC.
  12. L. R. Gray, S. J. Higgins, W. Levason and M. Webster, J. Chem. Soc., Dalton Trans., 1984, 1433 RSC; E. G. Hope, W. Levason, M. Webster and S. G. Murray, J. Chem. Soc., Dalton Trans., 1986, 1003 RSC.
  13. L. Y. Martin, C. R. Sperati and D. H. Busch, J. Am. Chem. Soc., 1977, 99, 2968 CrossRef CAS.
  14. W. Rosen and D. H. Busch, J. Am. Chem. Soc., 1969, 91, 4694 CrossRef CAS.
  15. A. B. P. Lever, Inorganic Electronic Spectroscopy, Elsevier, Amsterdam, 1984 Search PubMed; D. A. Rowley and R. S. Drago, Inorg. Chem., 1968, 7, 795 Search PubMed.
  16. W. Levason, C. A. McAuliffe and S. G. Murray, Inorg. Chim. Acta, 1976, 17, 247 CrossRef CAS.
  17. D. Reinen, C. Friebel and V. Propach, Z. Anorg. Allg. Chem., 1974, 408, 187 CrossRef CAS.
  18. A. J. Blake, M. A. Halcrow and M. Schröder, J. Chem. Soc., Dalton Trans., 1992, 2803 RSC.
  19. A. J. Blake, R. O. Gould, M. A. Halcrow, A. J. Holder, T. I. Hyde and M. Schröder, J. Chem. Soc., Dalton Trans., 1992, 3427 RSC.
  20. L. F. Warren and M. A. Bennett, Inorg. Chem., 1976, 15, 3126 CrossRef CAS; L. R. Gray, S. J. Higgins, W. Levason and M. Webster, J. Chem. Soc., Dalton Trans., 1984, 459 RSC.
  21. S. K. Harbron, S. J. Higgins, E. G. Hope, T. Kemmitt and W. Levason, Inorg. Chim. Acta, 1987, 130, 43 CrossRef CAS.
  22. N. L. Hill and H. Hope, Inorg. Chem., 1974, 13, 2079 CrossRef CAS.
  23. T. Ito, M. Kato and H. Ito, Bull. Chem. Soc. Jpn., 1984, 57, 2641 CAS and refs. therein.
  24. S. J. Higgins, W. Levason, M. C. Feiters and A. T. Steel, J. Chem. Soc., Dalton Trans., 1986, 317 RSC; L. R. Hanton, J. Evans, W. Levason, R. J. Perry and M. Webster, J. Chem. Soc., Dalton Trans., 1991, 2039 RSC.
  25. A. J. Blake, M. J. Bywater, R. D. Crofts, A. M. Gibson, G. Reid and M. Schröder, J. Chem. Soc., Dalton Trans., 1996, 2979 RSC.
  26. N. Binsted, S. L. Cook, J. Evans, G. N. Greaves and R. J. Price, J. Am. Chem. Soc., 1987, 109, 3669 CrossRef CAS; R. W. Joyner, K. J. Martin and P. Meehan, J. Phys. C, 1987, 20, 4005 CrossRef.
  27. D. J. Gulliver, E. G. Hope, W. Levason, S. G. Murray, D. M. Potter and G. L. Marshall, J. Chem. Soc., Perkin Trans. 2, 1984, 429 RSC.
  28. SHELXS 86, program for crystal structure solution, G. M. Sheldrick, Acta Crystallogr., Sect. A, 1990, 46, 467 Search PubMed.
  29. TEXSAN Crystal Structure Analysis Package, Molecular Structure Corporation, The Woodlands, TX, 1995.
  30. N. Binsted, PAXAS, Program for the analysis of X-ray absorption spectra, University of Southampton, 1988.
  31. N. Binsted, J. W. Campbell, S. J. Gurman and P. C. Stephenson, EXCURV 92, SERC Daresbury Laboratory, 1992.
Click here to see how this site uses Cookies. View our privacy policy here.