Neutral and cationic ruthenium hydrotris(pyrazolyl)borate derivatives containing bulky monodentate phosphines. Crystal structures of [RuTp(H2O)(PPri2Me)2][CF3SO3]·EtOH and [RuTp(N2)(PEt3)2][BPh4]

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Miguel A. Jiménez Tenorio, Manuel Jiménez Tenorio, M. Carmen Puerta and Pedro Valerga


Abstract

The complexes [RuTp(Cl)(PPri2Me)2] 1 and [RuTp(Cl)(PEt3)2] 2 were prepared by thermal displacement of PPh3 from [RuTp(Cl)(PPh3)2] by the corresponding phosphine. A series of cationic complexes of the type [RuTp(L)(PR3)2]+ (L = H2O, N2 or CNBut; PR3 = PPri2Me or PEt3) was obtained by chloride abstraction from 1 or 2 in the presence of L. As consequence of the steric crowding, one of the PPri2Me ligands in 1 is labile, and it was readily replaced by neutral molecules such as MeCN or CNBut to yield the neutral complexes [RuTp(Cl)L(PPri2Me)] (L = MeCN or CNBut). The monohydrides [RuTp(H)(PPri2Me)2] and [RuTp(H)(PEt3)2] were obtained by treatment of 1 or 2 with NaBH4 in MeOH. Protonation of these monohydrides led to the cationic dihydrogen complexes [RuTp(H2)(PPri2Me)2]+ and [RuTp(H2)(PEt3)2]+ which were isolated as [BPh4] salts, and characterized by determination of their (T1)min and 1JHD coupling constants in the corresponding isotopomers. The neutral hydride(dihydrogen) complex [RuTp(H)(H2)(PPri2Me)], which resulted from the reaction of [RuTp(Cl)(MeCN)(PPri2Me)] with NaBH4 in MeOH, was characterized in analogous fashion. The crystal structures of the complexes [RuTp(H2O)(PPri2Me)2][CF3SO3]·EtOH and [RuTp(N2)(PEt3)2][BPh4] were determined.


References

  1. C. Gemel, G. Trimmel, C. Slugovc, S. Kremel, K. Mereiter, R. Schmid and K. Kirchner, Organometallics, 1996, 15, 3998 CrossRef.
  2. C. Gemel, P. Wiede, K. Mereiter, V. N. Sapunov, R. Schmid and K. Kirchner, J. Chem. Soc., Dalton Trans., 1996, 4071 RSC.
  3. G. Trimmel, C. Slugovc, P. Wiede, K. Mereiter, V. N. Sapunov, R. Schmid and K. Kirchner, Inorg. Chem., 1997, 36, 1076 CrossRef CAS.
  4. C. Slugovc, P. Wiede, K. Mereiter, R. Schmid and K. Kirchner, Organometallics, 1997, 16, 2768 CrossRef CAS.
  5. K. Kirchner, personal communication.
  6. F. A. Jalón, A. Otero and A. Rodríguez, J. Chem. Soc., Dalton Trans., 1995, 1629 RSC.
  7. C. Slugovc, D. Doberer, C. Gemel, R. Schmid, K. Kirchner, B. Winkler and F. Stelzer, Monatsh. Chem., 1998, 129, 221 CrossRef CAS.
  8. N. W. Alcock, I. D. Burns, K. S. Claire and A. F. Hill, Inorg. Chem., 1992, 31, 2906 CrossRef CAS.
  9. C. Gemel, G. Kickelbick, R. Schmid and K. Kirchner, J. Chem. Soc., Dalton Trans., 1997, 2113 RSC.
  10. C. Slugovc, V. Sapunov, P. Wiede, K. Mereiter, R. Schmid and K. Kirchner, J. Chem. Soc., Dalton Trans., 1997, 4209 RSC.
  11. N.-Y. Sun and S. J. Simpson, J. Organomet. Chem., 1992, 434, 341 CrossRef CAS.
  12. W.-C. Chan, C.-P. Lau, Y.-Z. Chen, Y.-Q. Fang, S.-M. Ng and G. Jia, Organometallics, 1997, 16, 34 CrossRef CAS.
  13. M. A. Halcrow, B. Chaudret and S. Trofimenko, J. Chem. Soc., Chem. Commun., 1993, 465 RSC.
  14. B. Moreno, S. Sabo-Etienne, B. Chaudret, A. Rodríguez-Fernández, F. A. Jalón and S. Trofimenko, J. Am. Chem. Soc., 1995, 117, 7441 CrossRef CAS.
  15. M. Jiménez-Tenorio, M. A. Jiménez Tenorio, M. C. Puerta and P. Valerga, Inorg. Chim. Acta, 1997, 259, 77 CrossRef CAS.
  16. C. Slugovc, K. Mereiter, E. Zobetz, R. Schmid and K. Kirchner, Organometallics, 1996, 15, 5275 CrossRef CAS.
  17. M. Jiménez-Tenorio, M. A. Jiménez Tenorio, M. C. Puerta and P. Valerga, Organometallics, 1997, 16, 5528 CrossRef CAS.
  18. (a) I. de los Ríos, M. Jiménez Tenorio, J. Padilla, M. C. Puerta and P. Valerga, Organometallics, 1996, 15, 4565 CrossRef; (b) I. de los Ríos, M. Jiménez Tenorio, M. C. Puerta and P. Valerga, J. Am. Chem. Soc., 1997, 119, 6529 CrossRef CAS and refs. therein.
  19. S. Trofimenko, Inorg. Synth., 1970, 12, 99 CAS.
  20. P. T. Beurskens, DIRDIF, Technical Report 1984/1, Crystallography Laboratory, Toernooiveld, 1984.
  21. TEXSAN, Single-Crystal Structure Analysis Software, version 5.0, Molecular Structure Coorporation, Houston, TX, 1989.
  22. C. K. Johnson, ORTEP, A Thermal Ellipsoid Plotting Program, Oak Ridge National Laboratory, Oak Ridge, TN, 1965.
  23. M. Jiménez Tenorio, J. Padilla, M. C. Puerta and P. Valerga, unpublished work.
  24. B. K. Campion, R. H. Heyn and T. D. Tilley, J. Chem. Soc., Chem. Commun., 1988, 278 RSC; T. Arliguie, C. Border, B. Chaudret, J. Devillers and R. Poilblanc, Organometallics, 1989, 8, 1308 CrossRef CAS.
  25. T. J. Johnson, K. Foltig, W. E. Streib, J. D. Martin, J. C. Huffman, S. A. Jackson, O. Eisenstein and K. G. Caulton, Inorg. Chem., 1995, 34, 488 CrossRef CAS.
  26. C. Bohanna, M. A. Esteruelas, A. V. Gómez, A. M. López and M. P. Martínez, Organometallics, 1997, 16, 4464 CrossRef CAS.
  27. I. D. Burns, A. F. Hill, A. J. P. White, D. J. Williams and J. D. E. T. Wilton-Ely, Organometallics, 1998, 17, 1552 CrossRef CAS.
  28. A. Llobet, D. J. Hodgson and T. J. Meyer, Inorg. Chem., 1990, 29, 3760 CrossRef CAS.
  29. Y.-Z. Cheng, W.-C. Chan, C.-P. Lau, H.-S. Chu, H.-L. Lee and G. Jia, Organometallics, 1997, 16, 1241 CrossRef.
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