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DOI: 10.1039/A606432I (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1997, 443-448

Dynamic behaviour of SO2 and NO ligands in hexanuclear ruthenium clusters as probed by 1H NMR signals of a coexisting µ-allyl ligand

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Teiji Chihara, Aldo Jesorka, Hidenori Ikezawa and Yasuo Wakatsuki

Abstract

A hexanuclear ruthenium carbide carbonyl cluster with SO2 and µ-η3-C3H5 ligands, [Ru6C(CO)14(SO2)(µ-η3-C 3H5)]- shows fluxionality with ΔH‡ = 7.3 kcal mol-1 and ΔS‡ = -16.6 cal K-1 mol-1 as observed by variable-temperature 1H NMR spectroscopy of the syn- and anti-protons of the µ-η3-C3H5 moiety. Likewise, fluxionality of a neutral cluster complex with NO and allyl groups, [Ru6C(CO)14(NO)(µ-η3-C3 H5)], has been found to have ΔH‡ = 9.5 kcal mol-1 and ΔS‡ = -7.8 cal K-1 mol-1. The 2-methoxycarbonylallyl analogue of [Ru6C(CO)14(NO)(µ-η3-C3 H4CO2Me)], exhibits similar fluxional behaviour with virtually identical parameters (ΔH‡ = 9.2 kcal mol-1 and ΔS‡ = -7.1 cal K-1 mol-1), while model analysis based on its single-crystal structure indicates that rotation of the η3-co-ordinated allyl group would have a very high steric barrier. The observed dynamic behaviour was thus concluded to arise from rapid migration of the SO2 or NO ligand over the metal atoms in the cluster core.

References

  1. J. L. Vidal, W. E. Walker and R. C. Schoening, Inorg. Chem., 1981, 20, 238 CrossRef CAS; A. Fumagalli, S. Martinengo, G. Ciani, A. Sironi and B. T. Heaton, J. Chem. Soc., Dalton Trans., 1988, 163 RSC; S. R. Drake, B. F. G. Johnson and J. Lewis, J. Chem. Soc., Dalton Trans., 1988, 1517 RSC; A. Fumagalli, R. D. Pergola, F. Bonacina, L. Garlaschelli, M. Moret and A. Sironi, J. Am. Chem. Soc., 1989, 111, 165 CrossRef CAS; B. F. G. Johnson, R. Khatta, J. Lewis, P. R. Raithby and M. J. Rosales, J. Organomet. Chem., 1990, 385, 387 CrossRef CAS; A. Fumagalli, S. Martinengo, G. Ciani, M. Moret and A. Sironi, Inorg. Chem., 1992, 31, 2900 CrossRef CAS; S. P. Tunik, V. R. Krym, G. L. Starova, A. B. Nikol'skii, I. S. Podkorytov, S. Ooi, M. Yamasaki and M. Shiro, J. Organomet. Chem., 1994, 481, 83 CrossRef CAS; B. F. G. Johnson, J. Lewis, H. Curtis, T. Adatia, M. McPartlin and J. Morris, J. Chem. Soc., Dalton Trans., 1994, 243 RSC; T. Blum, M. P. Brown, B. T. Heaton, A. S. Hor, J. A. Iggo, J. S. Z. Sabounchei and A. K. Smith, J. Chem. Soc., Dalton Trans., 1994, 513 RSC; C.-J. Su, Y. Chi, S.-M. Peng and G.-H. Lee, Organometallics, 1995, 14, 4286 CrossRef CAS.
  2. C. J. Brown, P. J. McCarthy and I. D. Salter, J. Chem. Soc., Dalton Trans., 1990, 3583 RSC.
  3. S. R. Drake, B. F. G. Johnson and J. Lewis, J. Organomet. Chem., 1988, 340, C31 CrossRef CAS; A. Fumagalli, S. Martinengo, V. G. Albano, D. Braga and F. Grepioni, J. Chem. Soc., Dalton Trans., 1989, 2343 RSC; C.-C. Chen, Y. Chi, S.-M. Peng and G.-H. Lee, J. Chem. Soc., Dalton Trans., 1993, 1823 RSC; C. E. Housecroft, D. M. Matthews, A. Waller, A. J. Edwards and A. L. Rheingold, J. Chem. Soc., Dalton Trans., 1993, 3059 RSC.
  4. S. A. R. Knox, B. R. Lloyd, D. A. V. Morton, S. M. Nicholls, A. G. Orpen, J. M. Viñas, M. Weber and G. K. Williams, J. Organomet. Chem., 1990, 394, 385 CrossRef CAS.
  5. C. J. Adams, M. I. Bruce, M. Schulz, B. W. Skelton and A. H. White, J. Organomet. Chem., 1994, 472, 285 CrossRef CAS.
  6. A. J. Blake, A. H. Harrison, B. F. G. Johnson, E. J. L. McInnes, S. Parsons, D. S. Shephard and L. J. Yellowlees, Organometallics, 1995, 14, 3160 CrossRef CAS.
  7. J. Washington and J. Takats, Organometallics, 1990, 9, 925 CrossRef CAS; L. J. Farrugia and S. E. Rae, Organometallics, 1992, 11, 196 CrossRef CAS; C. P. Casey, R. A. Windenhoefer, S. L. Hallenbeck, R. K. Hayashi and J. A. Gavney, jun., Organometallics, 1994, 13, 4720 CrossRef CAS; D. Wang, H. Shen, M. G. Richmond and M. Schwartz, Organometallics, 1995, 14, 3636 CrossRef CAS.
  8. T. Inui, S. Iwamoto and S. Shimizu, Proc. 9th Int. Zeolite Conf., 1992, II, 405 Search PubMed.
  9. T. Chihara, K. Sawamura, H. Ikezawa, H. Ogawa and Y. Wakatsuki, Organometallics, 1996, 15, 415 CrossRef CAS.
  10. T. Chihara, K. Sawamura, H. Ogawa and Y. Wakatsuki, J. Chem. Soc., Chem. Commun., 1994, 1179 RSC.
  11. T. Chihara and Y. Wakatsuki, unpublished work.
  12. P. L. Bogdan, M. Sabat, S. A. Sunshine, C. Woodcock and D. F. Shriver, Inorg. Chem., 1988, 27, 1904 CrossRef CAS.
  13. G. J. Kubas, Acc. Chem. Res., 1994, 27, 183 CrossRef CAS.
  14. G. B. Karet, C. L. Stern, D. M. Norton and D. F. Shriver, J. Am. Chem. Soc., 1993, 113, 9979 CrossRef.
  15. D. S. Stephenson and G. Binsch, Quantum Chemistry Program Exchange, 1978, 10, 365 Search PubMed.
  16. A. C. T. North, D. C. Phillips and F. S. Mathews, Acta Crystallogr., Sect. A, 1968, 24, 351 CrossRef.
  17. D. T. Cromer and J. T. Waber, in International Tables for X-Ray Crystallography, eds. J. A. Ibers and W. C. Hamilton, Kynoch Press, Birmingham, 1974, vol. 4, p. 71 Search PubMed.
  18. D. T. Cromer, in International Tables for X-Ray Crystallography, eds. J. A. Ibers and W. C. Hamilton, Kynoch Press, Birmingham, 1974, vol. 4, p. 148 Search PubMed.
  19. P. Main, S. E. Hull, L. Lessinger, G. Germain, J.-P. Declerq and M. M. Woolfson, MULTAN 78, University of York, 1978.
  20. T. Sakurai and K. Kobayashi, Rikagaku Kenkyusho Hokoku, 1979, 55, 69 Search PubMed.
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