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Li+(TMPAND)Na−: The first alkalide prepared from an azacage complexant

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Abstract

The new lithium-selective complexant 5,12,17-trimethyl-1,5,9,12,17-pentaazabicyclo[7.5.5]nonadecane (TMPAND) was used to synthesize Li+(TMPAND)Na−, the first alkalide prepared from an azacage complexant. This sodide was characterized by a variety of methods. Differential scanning calorimetry experiments showed a reversible, endothermic, solid-solid phase transition at an onset temperature of −75 ± 3°C and with ΔH = 3.3 ± 1 kJ/mol.23Na NMR spectra showed a peak at −61 ppm, characteristic of a sodium anion, and a second minor peak at −10 ppm, probably due to the interaction of Na- with trapped electrons. The quadrupole coupling constant of the complexed lithium cation was found to be 0.19 MHz at −100°C, and7Li NMR spectra showed a discontinuity in the line width of the7Li NMR peak and in the quadrupole coupling constant at the phase transition.

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References

  1. For general reviews see: J. L. Dye:Science 247, 663 (1990); (b) J. L. Dye:Pure Appl. Chem. 61, 1555 (1989); (c) J. L. Dye:Proceedings of the The Robert A. Welch Foundation Conference on Chemical Research XXXII Valency, 65 (1988); (d) J. L. Dye and M. G. DeBacker:Ann. Rev Phys. Chem. 38, 271 (1987); (e) J. L. Dye:Scientific American 257, 66 (1987); (f) J. L. Dye.:Prog. Inorg. Chem. 32, 327 (1984).

    Google Scholar 

  2. J. L. Dye, M. G. DeBacker, and V. A. Nicely:J. Am. Chem. Soc. 92, 5226 (1970).

    Google Scholar 

  3. C. J. Pedersen:J. Am. Chem. Soc. 89, 2495 (1967); (b) C. J. Pedersen:J. Am. Chem. Soc. 89, 7017 (1967); (c) C. J. Pedersen: J. Incl. Phenom. 6, 337 (1988); (d) C. J. Pedersen and H. K. Frensdorff:Angew. Chem. Int. Ed. Engl. 11, 16 (1972).

    Google Scholar 

  4. J.-M. Lehn:J. Incl. Phenom. 6, 351 (1988), and references therein.

    Google Scholar 

  5. J. L. Dye, J. M. Ceraso, M. T. Lok, B. L. Barnett, and F. J. Tehan:J. Am. Chem. Soc. 96, 608 (1974).

    Google Scholar 

  6. A. Ellaboudy, J. L. Dye, and P. B. Smith:J. Am. Chem. Soc. 105, 6490 (1983); (b) S. B. Dawes, D. L. Ward, R. H. Huang, and J. L. Dye:J. Am. Chem. Soc. 108, 3534 (1986).

    Google Scholar 

  7. See also: R. H. Huang, D. L. Ward, and J. L. Dye:Acta Crystallogr. C C46, 1835 (1990); (b) J. L. Dye and R. H. Huang:Chem. Brit. 26, 239 (1990); (c) R. H. Huang, D. L. Ward, and J. L. Dye:J. Am. Chem. Soc. 111, 5707 (1989); (d) D. Issa and J. L. Dye:Inorg. Chim. Acta 160, 111 (1989); (e) R. S. Bannwart, S. A. Solin, M. G. DeBacker, and J. L. Dye:J. Am. Chem. Soc. 111, 5552 (1989); (f) M. E. Kuchenmeister and J. L. Dye:J. Am. Chem. Soc. 111, 935 (1989); (g) D. L. Ward, R. H. Huang, and J. L. Dye:Acta Crystallogr. C C44, 1374 (1988); (h) J. Papaioannou and J. L. Dye:Rev. Sci. Instrum. 59, 496 (1988); (i) R. Concepcion and J. L. Dye:J. Am. Chem. Soc. 109, 7203 (1987); (j) F. J. Tehan, B. L. Barnett, and J. L. Dye:J. Am. Chem. Soc. 96, 7203 (1974). 8. K.-L. Tsai and J. L. Dye:J. Am. Chem. Soc. 113, 1650 (1991).

    Google Scholar 

  8. See for example: (a) A. G. M. Barrett, C. R. A. Godfrey, D. M. Hollinshead, P. Prokopiou, D. H. R. Barton, R. B. Boar, L. Joukhadar, J. F. McGhie, and S. C. Misra:J. Chem. Soc., Perki Trans I 11501 (1981); (b) G. P. Pez, I. L. Mador, J. E. Galle, R. K. Crissey, and C. E. Forbes:J. Am. Chem. Soc. 107, 4098 (1985); (c) Z. Jedlinski, M. Kowalczuk, and A. Misiolek:J. Chem. Soc., Chem. Commun. 1261 (1988); (d) T. Ohsawa, T. Kobayashi, Y. Mizuguchi, T. Saitoh, and T. Oishi:Tetrahedron Lett. 26, 6103 (1985); (e) D. J. Mathre and W. C. Guida:Tetrahedron Lett. 21, 4773 (1980).

  9. The IUPAC names are: 1,4,7,10,13,16-hexaaza-1,4,7,10,13,16-hexamethylcyclooctadecane (HMHCY, hexamethylhexacyclen); 1,4,7,10,13-pentaaza-1,4,7,10,13-pentamethylcyclopentadecane (PMPCY, pentamethylpentacyclen); and 1,4,7-triaza-1,4,7,-timethylcyclononane (TMTCY, trimethyltricyclen).

  10. For an example of the use of TMTCY as a complexing agent see: K. Wieghardt, S. Brodka, K. Peters, E. M. Peters, and A. Simon:Z. Naturforsch. B 42, 279 (1987).

    Google Scholar 

  11. J. L. Dye:J. Phys. Chem. 88, 3842 (1984).

    Google Scholar 

  12. J. J. Christensen, D. J. Eatough, and R. M. Izatt:Chem. Rev. 74, 351 (1974).

    Google Scholar 

  13. A. Bencini, A. Bianchi, M. Ciampolini, E. Garcia-Espana, P. Dapporto, M. Micheloni, P. Paoli, J. A. Ramirez, and B. Valtancoli:J. Chem. Soc., Chem. Commun. 701 (1989); (b) A. Bencini, A. Bianchi, A. Borselli, M. Ciampolini, E. Garcia-Espana, P. Dapporto, M. Micheloni, P. Paoli, J. A. Ramirez, and B. Valtancoli:Inorg. Chem. 28, 4279 (1989).

  14. J. Cheney and J.-M. Lehn:J. Chem. Soc., Chem. Commun. 487 (1972); (b) J. Chaney, J. P. Kintzinger, and J.-M. Lehn:Nouv. J. Chim. 2, 411 (1978).

  15. K. J. Moeggenborg: Ph.D. Dissertation, Michigan State University (1990); (b) K. J. Moeggenborg, J. Papaioannou, and J. L. Dye:Chem. Mater 3, 514 (1991).

  16. J. L. Dye, M. R. Yemen, M. G. DaGue, and J.-M. Lehn:J. Chem. Phys. 68, 1665 (1978).

    Google Scholar 

  17. H. E. Kissinger:J. Res. Nat. Bur. Stand. 57, 217 (1956).

    Google Scholar 

  18. J. M. Ceraso and J. L. Dye:J. Chem. Phys. 61, 1585 (1974); (b) J. L. Dye:J. Phys. Chem. 88 3842 (1984); (c) P. P. Edwards, A. Ellaboudy, D. M. Holton, and N. C. Pyper:Annu. Rep. NMR Spectroscopy 20, 315 (1988).

    Google Scholar 

  19. J. H. Van Vleck:Phys. Rev. 74, 1168 (1948).

    Google Scholar 

  20. D. Freude, T. A. Carpenter, J. Haase, J. Klinowski, and G. Roniker:Chem. Phys. Lett. 119, 365 (1985).

    Google Scholar 

  21. R. A. Logan, R. E. Cote, and P. Kusch:Phys. Rev. 86, 280 (1952).

    Google Scholar 

  22. N. F. Ramsey:Phys. Rev. 77, 567 (1950);78, 699 (1950);83, 540 (1951);86, 243 (1952).

    Google Scholar 

  23. M. A. Atamian: unpublished results, this laboratory.

  24. S. Doeuff, K.-L. Tsai, and J. L. Dye:Inorg. Chem. 30, 849 (1991).

    Google Scholar 

  25. J. S. Landers, J. L. Dye, A. Stacy, and M. J. Sienko:J. Phys. Chem. 85, 1096 (1981); (b) R. H. Huang, M. K. Faber, J. Kim, and J. L. Dye: unpublished results, this laboratory.

    Google Scholar 

  26. E. Mei, A. I. Popov, and J. L. Dye:J. Am. Chem. Soc. 99, 6532 (1977); (b) E. Kauffman, J. L. Dye, J.-M. Lehn, and A. I. Popov:J. Am. Chem. Soc. 102, 2274 (1980).

    Google Scholar 

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Authors and Affiliations

  1. Department of Chemistry, Michigan State University, 48824, East Lansing, Michigan, USA

    Judith L. Eglin, Evelyn P. Jackson, Kevin J. Moeggenborg & James L. Dye

  2. Department of Chemistry, University of Florence, via Maragliano 77, 50144, Florence, Italy

    Andrea Bencini & Mauro Micheloni

Authors
  1. Judith L. Eglin
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  2. Evelyn P. Jackson
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  3. Kevin J. Moeggenborg
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  4. James L. Dye
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  5. Andrea Bencini
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  6. Mauro Micheloni
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This paper is dedicated to the memory of the late Dr C. J. Pedersen.

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Eglin, J.L., Jackson, E.P., Moeggenborg, K.J. et al. Li+(TMPAND)Na−: The first alkalide prepared from an azacage complexant. J Incl Phenom Macrocycl Chem 12, 263–274 (1992). https://doi.org/10.1007/BF01053867

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  • DOI: https://doi.org/10.1007/BF01053867

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