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DOI: 10.1039/A702070H (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1997, 3553-3556

Synthesis and structure of osmium(II) organometallics incorporating a four-membered salicylideneiminium metallacycle and Os–η1-NO2 binding

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Kausikisankar Pramanik, Prasanta Ghosh and Animesh Chakravorty

Abstract

The reaction of (3-alkyliminio-5-methyl-2-oxidophenyl-C1,O)carbonylbromobis(triphenylphosphine)osmium(II), [Os(η2-LR)(PPh3)2(CO)Br] 1 (R = Me or Et) with NaNO2 furnished [Os(η2-LR)(PPh3)2(CO)(η1-NO2)]·H2O 2 (R = Me or Et) in excellent yields. Structure determination of the R = Et complex revealed that the LR ligand is C,O-chelated and the nitrite is N-bonded with two unequal N–O distances. The oxygen atom of the longer bond is involved in hydrogen bonding with the water molecule. The presence of the hydrogen-bonded iminium phenolato motif in LEt is consistent with 1H NMR and IR data. The Os–C bond lying trans to Os–NO2 in 2 (R = Et) is lengthened. In going from 1 to 2 a metal-to-ligand charge-transfer band and ν(C· · ·O) are shifted to higher frequencies and the OsIII–OsII reduction potential is shifted anodically. In contrast to 2, ruthenium affords [Ru(η1-LR)(PPh3)2(CO)(η2-O2N)] in which the nitrite ligand is O,O′-chelated. The origin of this differentiation is scrutinised.

References

  1. P. Ghosh, N. Bag and A. Chakravorty, Organometallics, 1996, 15, 3042 CrossRef CAS.
  2. N. Bag, S. B. Choudhury, A. Pramanik, G. K. Lahiri and A. Chakravorty, Inorg. Chem., 1990, 29, 5013 CrossRef CAS; N. Bag, S. B. Choudhury, G. K. Lahiri and A. Chakravorty, J. Chem. Soc., Chem. Commun., 1990, 1626 RSC.
  3. P. Ghosh, A. Pramanik and A. Chakravorty, Organometallics, 1996, 15, 4147 CrossRef CAS.
  4. A. S. Salomov, N. A. Parpiev, K. T. Sharipov, V. N. Kokunova, N. M. Sinitsyn and M. A. Porai-Koshits, Russ. J. Inorg. Chem., 1984, 29, 1633.
  5. P. Ghosh and A. Chakravorty, Inorg. Chem., 1997, 36, 64 CrossRef CAS.
  6. M. A. Hitchman and G. L. Rowbottom, Coord. Chem. Rev., 1982, 42, 55 CrossRef CAS; K. Nakamoto, Infrared and Raman Spectra of Inorganic and Coordination Compounds, 4th edn., Wiley, New York, 1986 Search PubMed.
  7. Z. Dawodi, M. J. Mays and P. R. Raithby, Acta Crystallogr., Sect. B, 1981, 37, 252 CrossRef.
  8. J. E. Huheey, E. A. Keiter and R. L. Keiter, Inorganic Chemistry: Principles of Structure and Reactivity, 4th edn., Harper Collins College Publishers, New York, 1993 Search PubMed.
  9. R. A. Leising, S. A. Kubow, M. R. Churchill, L. A. Buttrey, J. W. Ziller and K. J. Takeuchi, Inorg. Chem., 1990, 29, 1306 CrossRef CAS; A. J. Blake, R. O. Gould, B. F. G. Johnson and E. Parisini, Acta Crystallogr., Sect. C, 1992, 48, 982 CrossRef; M. A. A. F. de C. T. Carrondo, P. R. Rudolf, A. C. Skapski, J. R. Thornback and G. Wilkinson, Inorg. Chim. Acta, 1977, 24, L95 CrossRef; D. Ooyama, N. Nagao, H. Nagao, Y. Miura, A. Hasegawa, K.-I. Ando, F. S. Howell, M. Mukaida and K. Tanaka, Inorg. Chem., 1995, 34, 6024 CrossRef CAS.
  10. M. Haga, K. Isobe, S. R. Boone and C. G. Pierpont, Inorg. Chem., 1990, 29, 3795 CrossRef CAS.
  11. C. Sandorfy and D. Vocelle, Molecules in Physics, Chemistry and Biology, Kluwer, 1989, vol. 4, 195 Search PubMed.
  12. H. Bohme and M. Haake, Advances in Organic Chemistry, eds. H. Bohme and H. G. Viehe, Interscience, New York, 1976, part 1, vol. 9, p. 1 Search PubMed.
  13. G. M. Sharma and O. A. Roels, J. Org. Chem., 1973, 38, 3648 CAS.
  14. C. E. Johnson, jun. and F. A. Bovey, J. Chem. Phys., 1958, 29, 1012 CrossRef CAS.
  15. P. Ghosh, Ph.D. Thesis, Jadavpur University, Calcutta, 1995.
  16. L. Pauling, The Nature of the Chemical Bond and the Structure of Molecules and Crystals, 3rd edn., Cornell University Press, Ithaca, NY, 1960 Search PubMed.
  17. T. Hasegawa, M. Sekine, W. P. Schaefer and H. Taube, Inorg. Chem., 1991, 30, 449 CrossRef CAS; H. Taube, Pure Appl. Chem., 1991, 63, 651 CAS; W. D. Herman and H. Taube, J. Am. Chem. Soc., 1987, 109, 8101 CrossRef; H. Taube, Pure Appl. Chem., 1979, 51, 901 CAS.
  18. F. A. Cotton, Chemical Applications of Group Theory, Wiley Eastern Limited, New Delhi, 1971 Search PubMed.
  19. P. R. Hoffman and K. G. Caulton, J. Am. Chem. Soc., 1975, 99, 4221 CrossRef.
  20. F. Ullman and K. Brittner, Chem. Ber., 1909, 42, 2539 Search PubMed; R. R. Gagne, C. L. Spiro, T. J. Smith, C. A. Hamann, T. Thies and A. K. Shiemke, J. Am. Chem. Soc., 1981, 103, 4073 CrossRef CAS.
  21. P. Ghosh, A. Pramanik, N. Bag, G. K. Lahiri and A. Chakravorty, J. Organomet. Chem., 1993, 454, 237 CrossRef CAS.
  22. A. C. T. North, D. C. Phillips and F. A. Mathews, Acta Crystallogr., Sect. A, 1968, 24, 351 CrossRef.
  23. G. M. Sheldrick, SHELTXTL PLUS, Structure Determination Software Programs, Siemens Analytical X-Ray Instruments, Madison, WI, 1990.
  24. H. Margenau and G. M. Murphy, The Mathematics of Physics and Chemistry, D. Van Nostrand, Princeton, NJ, 1956 Search PubMed.
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