View PDF Version
 
DOI: 10.1039/A805494K (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1998, 3731-3736

Synthesis, X-ray crystal structure and spectroscopic characterization of the new dithiolene [Pd(Et2timdt)2] and of its adduct with molecular diiodine [Pd(Et2timdt)2]·I2·CHCl3 (Et2timdt = monoanion of 1,3-diethylimidazolidine-2,4,5-trithione)

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

Massimiliano Arca, Francesco Demartin, Francesco A. Devillanova, Alessandra Garau, Francesco Isaia, Francesco Lelj, Vito Lippolis, Samuele Pedraglio and Gaetano Verani

Abstract

The first Pd dithiolene [Pd(Et2timdt)2] 4a belonging to the new class of metal dithiolenes deriving from the R12timdt (R12timdt = monoanion of 1,3-dialkylimidazolidine-2,4,5-trithione) ligand has been characterised by X-ray crystal structure determination on a single crystal [monoclinic, space group P21/n, a = 9.545(2), b = 5.417(2), c = 20.093(4) Å, β = 93.40(2)°, Z = 2], UV–VIS–NIR, diffuse solid state reflectance, FTIR, FT-Raman spectroscopies, solid state 13C NMR and cyclic voltammetry and the results have been comparatively discussed with those obtained for the analogous [Ni(Et2timdt)2] 4b. The UV–VIS–NIR spectrum of 4a is dominated by a very intense absorption band at 1010 nm (ε = 70 000 dm3 mol–1 cm–1). The NIR features of 4a and 4b have been examined on the basis of the electronic structure of their ground-state configurations, investigated by DFT calculations. The co-crystallisation of 4a with I2 yielded the [Pd(Et2timdt)2]·I2·CHCl3 6 adduct [monoclinic, space group C2/m, a = 21.724(9), b = 12.901(4), c = 11.004(6) Å, β = 102.83(4)°, Z = 4]. No short metal–metal interaction was observed in both 4a and 6 (Pd[hair space][hair space]· · ·[hair space][hair space]Pd 5.42 Å in 4a and 5.25 Å in 6), since each palladium ion is almost ‘sandwiched’ between two imidazolidine rings of parallel adjacent molecules.

References

  1. J. R. Ferraro and J. M. Williams, Introduction to Synthetic Electrical Conductors, Academic Press, New York, 1987 Search PubMed; T. Nakamura, A. E. Underhill, A. T. Coomber, R. H. Friend, H. Tajima, A. Kobayashi and H. Kobayashi, Inorg. Chem., 1995, 34, 870 Search PubMed.
  2. J. A. McCleverty, Prog. Inorg. Chem., 1968, 10, 49 CAS; A. Sato, H. Kobayashi, T. Naito, F. Sakai and A. Kobayashi, Inorg. Chem., 1997, 36, 5262 CrossRef CAS; A. E. Pullen, S. Zeltner, R. M. Olk, E. Hoyer, K. A. Abboud and J. R. Reynolds, Inorg. Chem., 1997, 36, 4163 CrossRef CAS and refs. therein.
  3. U. T. Mueller-Westerhoff, B. Vance and D. I. Yoon, Tetrahedron, 1991, 47, 909 CrossRef CAS; M. Bousseau, L. Valade, J. P. Legros, P. Cassoux, M. Garbauskas and L. V. Interrante, J. Am. Chem. Soc., 1986, 108, 1908 CrossRef CAS; A. Kobayashi, H. Kim, Y. Sasaki, K. Murata, R. Kato and H. Kobayashi, J. Chem. Soc., Faraday Trans., 1990, 86, 361 RSC.
  4. R. Williams, E. Billig, J. H. Waters and H. B. Gray, J. Am. Chem. Soc., 1966, 88, 43 CrossRef CAS.
  5. U. T. Mueller-Westerhoff and B. Vance, Comp. Coord. Chem., 1987, 2, 595 Search PubMed; D. I. Yoon, PhD Thesis, University of Connecticut, 1988.
  6. K. W. Browall and L. V. Interrante, J. Coord. Chem., 1973, 3, 27 CAS.
  7. G. N. Schrauzer and V. P. Mayweg, J. Am. Chem. Soc, 1965, 87, 3585 CrossRef CAS.
  8. F. Bigoli, P. Deplano, F. A. Devillanova, V. Lippolis, P. J. Lukes, M. L. Mercuri, M. A. Pellinghelli and E. F. Trogu, J. Chem. Soc., Chem. Commun., 1995, 371 RSC.
  9. F. Bigoli, P. Deplano, F. A. Devillanova, J. R. Ferraro, V. Lippolis, P. J. Lukes, M. L. Mercuri, M. A. Pellinghelli and E. F. Trogu, Inorg. Chem., 1997, 36, 1218 CrossRef.
  10. K. H. Drexage and U. T. Mueller-Westerhoff, IEEE J. Quantum Electron, 1972, QE-8, 759 CrossRef; US Pat., 3 743 964, 1973 Search PubMed; P. N. Prasad and D. J. Williams, Introduction to Non-linear Optical Effects in Molecules and Polymers, Wiley, New York, 1991, p. 222 Search PubMed.
  11. J. Labanowsky and J. Andzelm, Density Functional Methods in Chemistry, Springer-Verlag, New York, 1991 Search PubMed.
  12. T. Ziegler, Chem. Rev., 1991, 91, 651 CrossRef CAS and refs. therein.
  13. A. C. Scheiner, J. Baker and J. W. Andzelm, J. Comput. Chem., 1997, 18, 775 CrossRef CAS.
  14. A. D. Becke, J. Chem. Phys., 1993, 98, 1372; 5648 CrossRef CAS.
  15. C. Lee, W. Yang and R. G. Parr, Phys. Rev. B, 1988, 37, 785 CrossRef CAS.
  16. Gaussian 94 (Revision D.1 & E.1), M. J. Frisch, G. W. Trucks, H. B. Schlegel, P. M. W. Gill, B. G. Johnson, M. A. Robb, J. R. Cheeseman, T. A. Keith, G. A. Petersson, J. A. Montgomery, K. Raghavachari, M. A. Al-Laham, V. G. Zakrzewski, J. V. Ortiz, J. B. Foresman, C. Y. Peng, P. Y. Ayala, M. W. Wong, J. L. Andres, E. S. Replogle, R. Gomperts, R. L. Martin, D. J. Fox, J. S. Binkley, D. J. Defrees, J. Baker, J. P. Stewart, M. Head-Gordon, C. Gonzalez and J. A. Pople, Gaussian, Inc., Pittsburgh PA, 1995.
  17. A. Schafer, H. Horn and R. Ahlrichs, J. Chem. Phys., 1992, 97, 2571 CrossRef.
  18. P. J. Stoffel, J. Org. Chem., 1964, 29, 2794 CAS.
  19. A. C. North, D. C. Phillips and F. S. Mathews, Acta Crystallogr., Sect. A, 1968, 24, 351 CrossRef.
  20. D. T. Cromer and J. T. Waber, International Tables for X-Ray Crystallography, The Kynoch Press, Birmingham, 1974, vol. IV, Table 2.2B Search PubMed.
  21. D. T. Cromer, International Tables for X-Ray Crystallography, The Kynoch Press, Birmingham, 1974, vol. IV, Table 2.3.1 Search PubMed.
  22. B. Frenz, Comp. Phys., 1988, 2, 42 Search PubMed; Crystallographic Computing, Oxford University Press, 1991, p. 126 Search PubMed.
  23. H. W. Roesky, H. Hofman, W. Clegg, M. Noltemeyer and G. M. Sheldrick, Inorg. Chem., 1982, 21, 3798 CrossRef CAS.
  24. R. Isaksson, T. Liljefors and J. Sandstrom, J. Chem. Res. (S), 1981, 43 Search PubMed.
  25. P. J. Stoffel, J. Org. Chem., 1964, 29, 2794 CAS.
  26. S. Sheibe, B. J. Pedersen and S.-O. Lawesson, Bull. Soc. Chim. Belg., 1978, 87, 229.
  27. F. Bigoli, M. A. Pellinghelli, D. Atzei, P. Deplano and E. F. Trogu, Phosphorus Sulfur, 1987, 37, 189 Search PubMed.
  28. M. Arca, A. Cornia, F. A. Devillanova, A. C. Fabretti, F. Isaia, V. Lippolis and G. Verani, Inorg. Chim. Acta, 1997, 262, 81 CrossRef CAS.
  29. S. Alvarez, R. Vicente and R. Hoffmann, J. Am. Chem. Soc., 1985, 107, 6253 CrossRef CAS.
  30. K. W. Browall and L. V. Interrante, J. Coord. Chem., 1973, 3, 27 CAS.
  31. K. W. Browall, L. V. Interrante and J. S. Kasper, Inorg. Chem., 1972, 11, 1800 CrossRef CAS.
  32. P. Deplano, F. A. Devillanova, J. R. Ferraro, F. Isaia, V. Lippolis and M. L. Mercuri, Appl. Spectrosc., 1992, 46, 1625 CAS and refs. therein.
  33. S. I. Shupack, I. Billig, R. J. H. Clark, R. Williams and H. B. Gray, J. Am. Chem. Soc., 1964, 86, 4594 CrossRef CAS.
  34. Z. S. Herman, R. F. Kirchner, G. H. Loew, U. T. Mueller-Westerhoff, A. Nazzal and M. C. Zerner, Inorg. Chem., 1982, 21, 46 CrossRef CAS.
  35. C. Adamo and F. Lelj, J. Chem. Phys., 1995, 103, 10605 CrossRef CAS; F. Lelj, C. Adamo and V. Barone, Chem. Phys. Lett., 1994, 230, 189 CrossRef CAS.
  36. C. Daul, Int. J. Quantum Chem., 1994, 52, 867 CrossRef CAS.
  37. I. Fischer-Hjalmars and A. Henriksson-Enflo, Int. J. Quantum. Chem., 1980, 18, 409 CAS; D. Demoulin, I. Fischer-Hjalmars, A. Henriksson Enflo, J. A. Pappas and M. Sandbom, Int. J. Quantum. Chem., 1977, 12(Suppl. 1), 351.
  38. J. A. Pople, D. Beveridge and P. Dobosh, J. Chem. Phys., 1967, 47, 2026 CrossRef CAS.
  39. R. J. H. Clark and P. C. Turtle, J. Chem. Soc., Dalton Trans., 1977, 2142 RSC.
  40. G. Steimecke, H. J. Sieler, R. Kirmse and E. Hoyer, Phosphorus Sulfur, 1979, 7, 49 Search PubMed.
  41. R. Kato, H. Kobayashi, A. Kobayashi and Y. Sasaki, Bull. Chem. Soc. Jpn., 1986, 59, 627 CAS.
  42. B. Pomarède, B. Garreau, I. Malfant, L. Valade, P. Cassoux, J. P. Legros, A. Audouard, L. Brossard, J. P. Ulmet, M. L. Doublet and E. Canadell, Inorg. Chem., 1994, 33, 3401 CrossRef CAS.
  43. H. Fujiwara, E. Arai and H. Kobayashi, Chem. Commun., 1997, 837 RSC.
Click here to see how this site uses Cookies. View our privacy policy here.