View PDF Version
 
DOI: 10.1039/A906276I (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1999, 4193-4201

Formation, characterization, and structural studies of novel thiosemicarbazone palladium(II) complexes. Crystal structures of [{Pd[C6H4C(Et)[double bond, length half m-dash]NN[double bond, length half m-dash]C(S)NH2]}4], [Pd{C6H4C(Et)[double bond, length half m-dash]NN[double bond, length half m-dash] C(S)NH2}(PMePh2)] and [{Pd[C6H4C(Et)[double bond, length half m-dash]NN[double bond, length half m-dash]C(S)NH2]}2(µ-Ph2PCH2PPh2)]

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

José M. Vila, Ma Teresa Pereira, Juan M. Ortigueira, María Graña, Darío Lata, Antonio Suárez, Jesús J. Fernández, Alberto Fernández, Margarita López-Torres and Harry Adams

Abstract

The reaction of thiosemicarbazones 4-MeC6H4C(Me)[double bond, length half m-dash]NN(H)C([double bond, length half m-dash]S)NH2 a, C6H5C(Et)[double bond, length half m-dash]NN(H)C([double bond, length half m-dash]S)NH2 b and 4-MeC6H4C(Me)[double bond, length half m-dash]NN(H)C([double bond, length half m-dash]S)NHMe c with K2[PdCl4] led to tetranuclear palladium(II) compounds, [{Pd[4-MeC6H3C(Me)[double bond, length half m-dash]NN[double bond, length half m-dash]C(S)NH2]}4], 1a, [{Pd[C6H4C(Et)[double bond, length half m-dash]NN[double bond, length half m-dash]C(S)NH2]}4] 1b, and [{Pd[4-MeC6H3C(Me)[double bond, length half m-dash] NN[double bond, length half m-dash]C(S)NHMe]}4] 1c; the ligands are tridentate through the [C, N, S[hair space][hair space]] atoms and they are deprotonated at the NH group. The Pd–Schelating bond is sufficiently strong for the complexes to undergo reactions with nucleophiles without bond cleavage. The molecular structure of 1b has been determined by single-crystal diffraction, confirming the formation of the tetranuclear moieties. Hydrogen bonding N[hair space][hair space]· · ·[hair space][hair space]H and S[hair space][hair space]· · ·[hair space][hair space]H links Pd4 clusters into strands in the solid state. Reaction of 1a and 1b with phosphines gave mono- and di-nuclear species, 2a, 2b, 3b and 5a, 5b, respectively. Treatment with 1,1′-bis(diphenylphosphino)ferrocene led to trimetallic compounds 6a and 6b. The molecular structure of 3b has been determined by X-ray crystallography; dimer units are present through N[hair space][hair space]· · ·[hair space][hair space]H hydrogen bonds. The reaction of 2b with hydrochloric acid resulted in a 1∶1 electrolyte, 4b, with NH and C[double bond, length half m-dash]S groups. Alternatively, treatment of 1a, 1b and 1c with strong chelating phosphines produced mononuclear compounds with only cleavage of the Pd–Sbridging bonds, 7a, 7b, 7c and 8c with the diphosphine monodentate; 7a and 7b were obtained with the dinuclear species 7a′ and 7b′, respectively, as impurities, where the bidentate phosphine ligand bridges two metallated units. The crystal structure of one such compound, 7b′, with a bridging bis(diphenylphosphino)methane ligand, is also described.

References

  1. I. Omae, Organometallic-coordination Compounds, Elsevier, Amsterdam, New York, 1986 Search PubMed.
  2. V. V. Dunina, O. A. Zalevskaya and V. M. Potapov, Russ. Chem. Rev., 1984, 571, 250 Search PubMed.
  3. G. R. Newkome, W. E. Puckett, W. K. Gupta and G. E. Kiefer, Chem. Rev., 1986, 86, 451 CrossRef CAS.
  4. A. D. Ryabov, Chem. Rev., 1990, 90, 403 CrossRef CAS.
  5. M. Pfeffer, Recl. Trav. Chim. Pays-Bas, 1990, 109, 567 CrossRef CAS.
  6. M. Pfeffer, J. P. Sutter, M. A. Rottvel, A. de Cian and J. Fischer, Tetrahedron, 1992, 48, 2440 CrossRef.
  7. A. Bose and C. H. Saha, J. Mol. Catal., 1989, 49, 271 CrossRef CAS.
  8. J. M. Vila, M. Gayoso, M. T. Pereira, M. López Torres, J. J. Fernández, A. Fernández and J. M. Ortigueira, J. Organomet. Chem., 1997, 532, 171 CrossRef CAS.
  9. J. M. Vila, M. T. Pereira, J. M. Ortigueira, D. Lata, M. López Torres, J. J. Fernández, A. Fernández and H. Adams, J. Organomet. Chem., 1998, 566, 93 CrossRef CAS.
  10. J. M. Vila, M. T. Pereira, J. M. Ortigueira, M. López Torres, A. Castiñeiras, J. J. Fernández, A. Fernández and D. Lata, J. Organomet. Chem., 1998, 556, 21 CrossRef CAS.
  11. R. G. Pearson, J. Am. Chem. Soc., 1963, 85, 3533 CrossRef CAS.
  12. P. Chattopadhyay, M. K. Nayak, S. P. Bhattacharyya and C. Sinha, Polyhedron, 1997, 16, 1291 CrossRef CAS.
  13. T. Kawamoto and Y. Kushi, Chem. Lett., 1992, 1057 CrossRef CAS.
  14. T. Kawamoto, I. Nagasawa, H. Kuma and Y. Kushi, Inorg. Chem., 1996, 35, 2427 CrossRef CAS.
  15. J. C. MacDonald and G. M. Whitsides, Chem. Rev., 1994, 94, 2383 CrossRef CAS.
  16. A. D. Burrows, C. W. Chan, M. M. Chowdhry, J. E. McGrady and D. M. P. Mingos, Chem. Soc. Rev., 1995, 24, 329 RSC.
  17. A. D. Burrows, D. M. P. Mingos, A. J. P. White and D. J. Williams, J. Chem. Soc., Chem. Commun., 1996, 97 RSC.
  18. (a) D. Kovala-Demertzi, A. Domopoulou, M. A. Demertzis, C. P. Raptopoulou and A. Terzis, Polyhedron, 1994, 13, 1917 CrossRef CAS; (b) D. Kovala-Demertzi, A. Domopoulou, M. A. Demertzis, J. Valdés-Martínez, S. Hernández-Ortega, G. Espinosa-Pérez, D. X. West, M. M. Salberg, G. A. Bain and P. D. Bloom, Polyhedron, 1996, 15, 665 CrossRef.
  19. J. M. Vila, M. Gayoso, M. T. Pereira, M. López-Torres, J. J. Fernández, A. Fernández and J. M. Ortigueira, J. Organomet. Chem., 1996, 506, 165 CrossRef CAS.
  20. T. S. Lobana, A. Sánchez, J. S. Casas, A. Castiñeiras, J. Sordo, M. S. García-Tasende and E. M. Vázquez-López, J. Chem. Soc., Dalton Trans., 1997, 4289 RSC.
  21. D. X. West, J. S. Ives, G. A. Bain, A. E. Liberta, J. Valdés-Martínez, K. H. Ebert and S. Hernández-Ortega, Polyhedron, 1997, 16, 1995 CrossRef.
  22. H. Onoue and I. Moritani, J. Organomet. Chem., 1972, 43, 431 CrossRef CAS; H. Onoue, K. Minami and K. Nakawaga, Bull. Chem. Soc. Jpn., 1970, 43, 3480 CrossRef.
  23. J. M. Vila, M. Gayoso, A. Fernández, N. Bailey and H. Adams, J. Organomet. Chem., 1993, 448, 233 CrossRef CAS.
  24. P. S. Pregosin and R. W. Kuntz, in 31P and 13C NMR of Transition Metal Phosphine Complexes, eds. P. Diehl, E. Fluck and R. Kosfeld, Springer, Berlin, 1979 Search PubMed.
  25. J. Albert, M. Gómez, J. Granell and J. Sales, Organometallics, 1990, 9, 1405 CrossRef CAS; R. Bosque, J. Granell, J. Sales, M. Font-Bardía and X. Solans, J. Organomet. Chem., 1994, 453, 147 CrossRef; J. Albert, J. Granell, J. Sales, M. Font-Bardía and X. Solans, Organometallics, 1995, 14, 1393 CrossRef.
  26. L. Pauling. The Nature of the Chemical Bond, Cornell University Press, New York, 3rd edn., 1960 Search PubMed.
  27. J. M. Vila, M. Gayoso, M. T. Pereira, A. Romar, J. J. Fernández and M. Thornton-Pett, J. Organomet. Chem., 1991, 401, 385 CrossRef CAS.
  28. J. Selbin, K. Abboud, S. F. Watkins, M. A. Gutirérrez and F. R. Fronczek, J. Organomet. Chem., 1983, 241, 259 CrossRef CAS; C. Navarro-Ranninger, I. López-Solera, A. Alvarez-Valdés, J. H. Rodríguez-Ramos, J. R. Masaguer and J. L. García-Ruano, Organometallics, 1993, 12, 4104 CrossRef.
  29. D. D. Perrin, W. L. F. Armarego and D. P. Perrin, Purification of Laboratory Chemicals, 2nd edn., Pergamon, Oxford, 1983 Search PubMed.
  30. I. Colquhoun and W. MacFarlane, J. Chem. Soc., Dalton Trans., 1982, 1915 RSC.
  31. G. M. Sheldrick, SADABS. Program for empirical absorption correction of area detector data, University of Göttingen, 1996.
  32. G. M. Sheldrick, SHELXL 97, University of Göttingen, 1997.
  33. G. M. Sheldrick, SHELXL 93, University of Göttingen, 1993.
Click here to see how this site uses Cookies. View our privacy policy here.