View PDF Version
 
DOI: 10.1039/A900798I (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1999, 1937-1944

Technetium(V) and rhenium(V) complexes of biguanide derivatives. Crystal structures

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

Andrea Marchi, Lorenza Marvelli, Michela Cattabriga, Roberto Rossi, Maria Neves, Valerio Bertolasi and Valeria Ferretti

Abstract

Biguanidine ligands HLn (HL1 = 1,1-dimethylbiguanide, HL2 = 1-phenethylbiguanide, HL3 = 1-phenylbiguanide) formed disubstituted cationic oxo- and nitrido-complexes [MO(HLn)2]3+ (M = Tc or Re) and [TcN(HLn)2(H2O)]2+. They are characterised by the presence of a network of N–H[hair space][hair space]· · ·[hair space][hair space]X (X = Cl or H2O) intra- and inter-molecular hydrogen bonds. The imido precursor of ReV [Re(NMe)(PPh3)2Cl3] formed monosubstituted complexes [Re(NMe)(HL1,2)(PPh3)Cl]2+. In alkaline solutions deprotonation of ligands occurs and monocationic, disubstituted oxo- and imido-species [MO(Ln)2]+ (M = Tc or Re), [Re(NCH3)(L1,3)2]+ and neutral nitrido complexes [TcN(Ln)2] are obtained. Elemental analyses, FT-IR and NMR spectroscopy and conductivity measurements are consistent with the proposed formulations. Crystal structures of [TcO(L1)2]+ and [TcN(HL1)2(H2O)]2+ were determined. The former shows a square pyramidal geometry in which the C–N bond distances are equivalent and indicative of π delocalisation on the chelate ring. The latter displays a pseudo-octahedral geometry with a water molecule trans to the Tc[triple bond, length half m-dash]N multiple bond. The C–N bond distances inside the ligands (1.30 and 1.38 Å) are consistent with single and double bond character, and less π delocalisation through the whole ligands.

References

  1. (a) C. R. Saha, J. Inorg. Nucl. Chem., 1976, 38, 1635 CAS; (b) D. Sen, J. Chem. Soc. A, 1969, 2900 RSC.
  2. R. Rathke, Ber. Bunsenges. Phys. Chem., 1879, 12, 779 Search PubMed; F. Emich, Monatsh. Chem., 1883, 4, 409 Search PubMed.
  3. P. Ray, Chem. Rev., 1961, 61, 313 CrossRef CAS.
  4. S. Roychowdhury, M. K. Sipani and B. Sur, J. Indian Chem. Soc., 1988, 65, 718 Search PubMed.
  5. (a) L. Fabbrizzi, M. Michelon, P. Paoletti and G. Schwarzenbach, J. Am. Chem. Soc., 1977, 5574 CrossRef CAS; (b) A. A. Pinkerton and D. Schwarzenbach, J. Chem. Soc., Dalton Trans., 1978, 989 RSC.
  6. R. K. Ray, Polyhedron, 1989, 8, 7 CrossRef CAS; R. K. Ray and G. B. Kauffman, Inorg. Chim. Acta, 1990, 274, 237 CrossRef.
  7. S. L. Shapiro, V. A. Parrino, E. Rogow and L. Freedman, J. Am. Chem. Soc., 1959, 81, 3725 CrossRef CAS; S. L. Shapiro, V. A. Parrino and L. Freedman, J. Am. Chem. Soc., 1959, 81, 2220, 3728; C. R. Sirtori and C. Pasik, Pharmacol. Res., 1994, 30, 187 CrossRef CAS.
  8. W. M. Watkins, J. D. Chulay, D. G. Sixsmith, H. C. Spencer and R. E. Howells, J. Pharm. Pharmacol., 1987, 39, 261 Search PubMed.
  9. P. Morain, C. Abraham, B. Portevin and G. De Nanteuil, Mol. Pharmacol., 1994, 46, 732 Search PubMed.
  10. M. Nicolini, G. Bandoli and U. Mazzi(Editors), Technetium and Rhenium in Chemistry and Nuclear Medicine 3, Cortina International Verona, Raven Press, New York, 1990 Search PubMed.
  11. S. R. Ernst and F. W. Cagle, Jr., Acta Crystallogr., Sect. B, 1977, 33, 235 CrossRef; C. J. Brown and L. Sengier, Acta Crystallogr., Sect. C, 1984, 40, 1294 CrossRef; M. Hriharan, S. S. Rajan and R. Srinivasan, Acta Crystallogr., Sect. C, 1989, 45, 911 CrossRef; S. R. Ernst, Acta Crystallogr., Sect. B, 1977, 33, 237 CrossRef.
  12. (a) P. V. Babykutty, C. P. Prabhakaran, R. Anantaraman and C. G. R. Nair, J. Inorg. Nucl. Chem., 1974, 36, 3685 CAS; (b) N. C. Ta and D. Sen, J. Inorg. Nucl. Chem., 1981, 43, 209 CAS; (c) O. C. Hart, S. G. Bott, J. L. Atwood and S. R. Cooper, J. Chem. Soc., Chem Commun., 1992, 894 RSC.
  13. (a) M. Cattabriga, A. Marchi, L. Marvelli, R. Rossi, G. Vertuani, R. Pecoraro, A. Scatturin, V. Bertolasi and V. Ferretti, J. Chem. Soc., Dalton Trans., 1998, 1453 RSC; (b) A. Marchi, L. Uccelli, L. Marvelli, R. Rossi, M. Giganti, V. Bertolasi and V. Ferretti, J. Chem. Soc., Dalton Trans., 1996, 3105 RSC.
  14. B. L. Haymore and G. V. Goeden, Inorg. Chem., 1983, 22, 157 CrossRef; G. K. Lahiri, S. Goswami, L. R. Falvello and A. Chakravorty, Inorg. Chem., 1987, 26, 3365 CrossRef CAS.
  15. C. K. Johnson, ORTEP II, Report ORNL-5138, Oak Ridge National Laboratory, Oak Ridge, TN, 1976.
  16. A. Marchi, L. Marvelli, R. Rossi, L. Magon, V. Bertolasi, V. Ferretti and P. Gilli, J.Chem. Soc., Dalton Trans., 1992, 1485 RSC; N. Bryson, J. C. Dewan, J. Lester-James, A. G. Jones and A. Davison, Inorg. Chem., 1988, 27, 2154 CrossRef CAS; T. N. Rao, D. Adhikesavalu, A. Camerman and A. R. Fritzberg, J. Am. Chem. Soc., 1990, 112, 5798 CrossRef CAS; A. Marchi, R. Rossi, L. Magon, A. Duatti, R. Pasqualini, V. Ferretti and V. Bertolasi, J. Chem. Soc., Dalton Trans., 1990, 1411 RSC.
  17. A. Marchi, A. Duatti, R. Rossi, L. Magon, R. Pasqualini, V. Bertolasi, V. Ferretti and G. Gilli, J. Chem. Soc., Dalton Trans., 1988, 1743 RSC; F. Tisato, U. Mazzi, G. Bandoli, G. Cros, M.-H. Darbieu, Y. Coulais and R. Guiraud, J. Chem. Soc., Dalton Trans., 1991, 1301 RSC; A. Marchi, R. Rossi, L. Marvelli and V. Bertolasi, Inorg. Chem., 1993, 32, 4673 CrossRef CAS; F. Tisato, F. Refosco and G. Bandoli, Coord. Chem. Rev., 1994, 135/136, 325 CrossRef and refs. therein.
  18. J. Baldas, S. F. Colmanet and G. A. Williams, Inorg. Chim. Acta, 1991, 179, 189 CrossRef CAS; A. Marchi, R. Rossi, L. Magon, A. Duatti, U. Casellato, R. Graziani, M. Vidal and F. Riche, J. Chem. Soc., Dalton Trans., 1990, 1935 RSC; V. Bertolasi, V. Ferretti, P. Gilli, A. Marchi and L. Marvelli, Acta Crystallogr., Sect. C, 1991, 47, 2535 CrossRef; Y. Kani, T. Takayama, S. Inomata, T. Sekine and H. Kudo, Chem. Lett., 1995, 1059 CAS.
  19. A. Marchi, P. Garuti, A. Duatti, L. Magon, R. Rossi, V. Ferretti and V. Bertolasi, Inorg. Chem., 1990, 29, 2097; S. Jurisson, E. O. Schlemper, D. E. Troutner, L. R. Canning, D. P. Nowotnik and R. D. Neirinckx, Inorg. Chem., 1986, 25, 543 CrossRef CAS; R. Faggiani, C. J. L. Lock, L. A. Epps, A. V. Kramer and H. D. Brune, Acta Crystallogr., Sect. C, 1990, 46, 2324 CrossRef; M. R. A. Pillai, C. S. John, J. M. Lo, E. O. Schlemper and D. E. Troutner, Inorg. Chem., 1990, 29, 1850 CrossRef CAS.
  20. T. C. Creitz, R. Gsell and D. L. Wampler, Chem Commun., 1969, 1371 RSC.
  21. K. Chakrabarty, T. Kar and S. P. Sen Gupta, Acta Crystallogr., Sect. C, 1990, 46, 2065 CrossRef.
  22. M. R. Snow, Acta Crystallogr., Sect. B, 1974, 30, 1850 CrossRef; D. Sen and S. Guha, J. Chem. Soc., Dalton Trans., 1975, 1701 RSC; C. H. L. Kennard, G. Smith and E. J. O'Reilly, Inorg. Chim. Acta, 1983, 77, L113 CrossRef CAS.
  23. M. Neves, L. Gano, M. J. Ribeiro, A. C. Santos, A. Marchi, C. S. Dimopolou and J. J. Pedroso de Lima, Nucl. Med. Biol., 1998, 26, 79 CrossRef.
  24. F. A. Cotton, A. Davison, V. W. W. Day, L. D. Gage and H. S. Trop, Inorg. Chem., 1979, 18, 3024 CrossRef CAS; A. Davison, C. Orvig, H. S. Trop, M. Shon, B. DePamphilis and A. G. Jones, Inorg. Chem., 1980, 19, 1988 CrossRef CAS; R. W. Thomas, M. J. Heeg, R. C. Helder and E. Deutsch, Inorg. Chem., 1985, 24, 1472 CrossRef CAS.
  25. J. Baldas, J. F. Boas, J. Bonnyman and G. A. Williams, J. Chem. Soc., Dalton Trans., 1984, 2395 RSC; J. Baldas, J. Bonnyman and G. A. Williams, Inorg. Chem., 1986, 25, 150 CrossRef CAS.
  26. D. Michos, X. L. Luo, J. A. K. Howard and R. H. Crabtree, Inorg. Chem., 1982, 31, 3914; J. Chatt and G. A. Rowe, J. Chem. Soc., 1962, 4019 RSC.
  27. J. Chatt, R. J. Dosser, F. King and G. J. Leigh, J. Chem. Soc., Dalton Trans., 1976, 2435 RSC.
  28. D. Karipides and W. C. Fernelius, Inorg. Synth., 1963, 7, 56 CAS.
  29. MOLEN, An Interactive Structure Solution Procedure, Enraf-Nonius, Delft, 1990; M. Nardelli, Comput. Chem., 1983, 7, 95 Search PubMed; D. T. Cromer and J. T. Waber, International Tables for X-Ray Crystallography, Kynoch Press, Birmingham, 1974, vol. 4 CrossRef CAS.