View PDF Version
 
DOI: 10.1039/A702963B (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1997, 2677-2680

Halide-abstraction reactions of tin(IV) and lanthanide(III) chlorides in tetrahydrofuran: crystal and molecular structures of [LnCl2(thf[hair space])5][SnCl5(thf [hair space])] where Ln = Ce, Gd or Yb

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

Gerald R. Willey, Timothy J. Woodman, David J. Carpenter and William Errington

Abstract

It has been established that halide abstraction from several lanthanide(III) chlorides can be effected by tin tetrachloride. Direct treatment (1∶1) of LnCl3 where Ln = Ce, Gd or Yb with SnCl4 in tetrahydrofuran (thf[hair space]) provided colourless compounds of the generic type LnSnCl7(thf[hair space])6 which have been identified by X-ray crystallography as ionic salts [trans-LnCl2(thf[hair space])5][SnCl5 (thf[hair space])]. The individual seven-co-ordinate cations feature a regular pentagonal-bipyramidal metal geometry in which a trans-LnCl2 unit is surrounded by five thf molecules arranged in an equatorial plane. These co-ordinated solvent molecules adopt the familiar ‘propeller-like’ arrangement indicative of a skew as opposed to envelope ligand conformation. For Ln = Ce, Ce–Cl 2.697(2), Ce–O mean 2.495(5) Å; for Ln = Gd, Gd–Cl 2.608(2), Gd–O mean 2.415(4) Å; for Ln = Yb, Yb–Cl 2.5375(13), Yb–O mean 2.346(4) Å. The six-co-ordinate [SnCl5(thf[hair space])]- anions common to the series show a two-fold axis of symmetry containing the metal atom, the oxygen (thf[hair space]) atom and a chloride atom mutually trans to the latter. Bond distances for Ln = Ce, i.e. Sn–O 2.276(7), Sn–Cl mean 2.399(2) Å, are typical for the series.

References

  1. P. P. K. Claire, G. R. Willey and M. G. B. Drew, J. Chem. Soc., Chem. Commun., 1987, 1100 RSC; P. N. Billinger, P. P. K. Claire, H. Collins and G. R. Willey, Inorg. Chim. Acta, 1988, 149, 63 CrossRef CAS.
  2. G. R. Willey, M. T. Lakin and N. W. Alcock, J. Chem. Soc., Chem. Commun., 1992, 1619 RSC; J. Chem. Soc., Dalton Trans., 1993, 3407 Search PubMed.
  3. G. R. Willey, P. R. Meehan, M. D. Rudd, H. J. Clase and N. W. Alcock, Inorg. Chim. Acta, 1994, 215, 209 CrossRef CAS.
  4. G. R. Willey, P. R. Meehan, P. A. Salter and M. G. B. Drew, Polyhedron, 1996, 15, 4227 CrossRef CAS.
  5. G. R. Willey, M. P. Spry and M. G. B. Drew, Polyhedron, 1996, 15, 4497 CrossRef CAS.
  6. G. R. Willey, M. L. Butcher, M. McPartlin and I. J. Scowen, J. Chem. Soc., Dalton Trans., 1994, 305 RSC; G. R. Willey, M. L. Butcher and M. G. B. Drew, J. Chem. Soc., Dalton Trans., 1994, 3285 RSC.
  7. G. R. Willey, M. L. Butcher, T. J. Woodman and M. G. B. Drew, J. Chem. Soc., Chem. Commun., 1994, 2721 RSC.
  8. G. R. Willey, T. J. Woodman and M. G. B. Drew, J. Organomet. Chem., 1996, 510, 213 CrossRef CAS.
  9. Z. Janas, P. Sobota and T. Lis, Polyhedron, 1988, 7, 2655 CrossRef CAS.
  10. Z. Janas, P. Sobota and T. Lis, J. Chem. Soc., Dalton Trans., 1991, 2429 RSC; P. Sobota, Polyhedron, 1992, 11, 715 CrossRef CAS.
  11. See, for example, G. R. Willey, T. J. Woodman and M. G. B. Drew, Polyhedron, 1997, 16, 3385 Search PubMed; L. E. Manzer, Inorg. Synth., 1982, 21, 139 CrossRef CAS; J. Shamir, Inorg. Chim. Acta, 1989, 156, 163 and refs. therein.
  12. G. M. Sheldrick, SADABS, Program for empirical absorption corrections, personal communication, 1996; R. H. Blessing, Acta Crystallogr., Sect. A, 1995, 51, 33 Search PubMed.
  13. SHELXTL PC, Version 5.0 Reference Manual, Siemens Industrial Autom. Inc., Analytical Instrumentation, Madison, WI, 1994 Search PubMed.
  14. G. M. Sheldrick, SHELXL 96, Program for Crystal Structure Refinement, University of Göttingen, 1996.
  15. SMART Software Reference Manual, Siemens Industrial Autom., Inc., Analytical Instrumentation, Madison, WI, 1994 Search PubMed.
  16. SAINT Software Reference Manual, Siemens Industrial Autom., Inc., Analytical Instrumentation, Madison, WI, 1995 Search PubMed.
  17. S. Anfang, K. Dehnicke and J. Magull, Z. Naturforsch., Teil B, 1996, 51, 531 CAS; G. R. Willey, P. R. Meehan, T. J. Woodman and M. G. B. Drew, Polyhedron, 1997, 16, 623 CrossRef CAS.
  18. P. Sobota, J. Utko and S. Szafert, Inorg. Chem., 1994, 33, 5203 CrossRef CAS.
  19. W. J. Evans, J. L. Shreeve, J. W. Ziller and R. J. Doedens, Inorg. Chem., 1995, 34, 576 CrossRef CAS.
  20. Z.-S. Jin, S.-C. Jin, X. Wang and W.-Q. Chen, J. Struct. Chem. (Jiegou Huaxue), 1988, 7, 181 Search PubMed.
  21. C. Castellani Bisi and V. Tazzoli, Acta Crystallogr., Sect. C, 1984, 40, 1832 CrossRef.
  22. G.-Y. Lin, Z.-S. Jin, Y.-M. Zhang and W.-Q. Chen, J. Organomet. Chem., 1990, 396, 307 CrossRef CAS.
  23. F.-X. Gao, G. Wei, Z.-S. Jin and W.-Q. Chen, J. Organomet. Chem., 1992, 438, 289 CrossRef CAS.
  24. G. B. Deacon, T. Feng, S. Nickel, B. W. Skelton and A. H. White, J. Chem. Soc., Chem. Commun., 1993, 1328 RSC.
  25. C.-T. Qian, B. Wang, D. Deng, C. Xu, X.-Y. Sun and R.-G. Ling, Jiegou Huaxue (J. Struct. Chem.), 1993, 12, 18 Search PubMed.
  26. Z. Hou, K. Kobayashi and H. Yamazaki, Chem. Lett., 1991, 265 CAS.
  27. Q. Shen, M.-H. Qi, J.-W. Guan and Y.-H. Lin, J. Organomet. Chem., 1991, 406, 353 CrossRef CAS.
Click here to see how this site uses Cookies. View our privacy policy here.