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DOI: 10.1039/A808023B (Paper) Reference Section for: Green Chem., 1999, 1, 31-32

Homogeneous dehydrosulfurisation under ambient conditions . Harnessing the facile polyhedral rearrangement in the ruthenium carbonyl cluster Ru5C(CO)15

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Alan J. Bailey, Sandeep Basra and Paul J. Dyson

Abstract

Reaction of the square pyramidal cluster Ru5C(CO)15 with H2S affords the bridged butterfly species (µ-H)Ru5C(CO)14(µ-SH) in which H and SH coordinate with simultaneous cleavage of one Ru–Ru bond and displacement of one CO. Subsequent reaction with CO regenerates the starting cluster and eliminates elemental sulfur (S8) and dihydrogen. These reactions take place at ambient temperatures and pressures.

References

  1. C. M. Friend and J. T. Roberts, Acc. Chem. Res., 1988, 21, 994.
  2. R. J. Angelici, Acc. Chem. Res., 1988, 21, 387 CrossRef CAS.
  3. J. H. Clark and D. J. Macquarrie, Chem. Commun., 1998, 853 RSC.
  4. D. A. Vicie and W. D. Jones, Organometallics, 1998, 17, 3411 CrossRef and references cited therein.
  5. P. Grancher, Hydrocarbon Process, 1978, 57, 155 Search PubMed.
  6. A. Shaver, M. El-khateeb and A.-M. Lebuis, Angew. Chem., Int. Ed. Engl., 1996, 35, 2362 CrossRef CAS.
  7. J. Gasiorek, F. Domka and P. Gasiorek, Przemysl Chem., 1998, 77, 304 Search PubMed.
  8. C. R. Eady, B. F. G. Johnson, J. Lewis and T. Mather, J. Organomet. Chem., 1973, 57, C82 CrossRef CAS.
  9. D. H. Farrar, P. F. Jackson, B. F. G. Johnson, J. Lewis, J. N. Nicholls and M. McPartlin, J. Chem. Soc., Chem. Commun., 1981, 415 RSC.
  10. B. F. G. Johnson, J. Lewis, J. N. Nicholls, J. Puga, P. R. Raithby, M. McPartlin and W. Clegg, J. Chem. Soc., Dalton Trans., 1983, 277 RSC.
  11. D. H. Farrar, A. J. Poë and Y. Zheng, J. Am. Chem. Soc., 1994, 116, 6252 CrossRef CAS.
  12. P. J. Dyson, Adv. Organomet. Chem., 1998, 43, 43 CAS.
  13. A. G. Cowie, B. F. G. Johnson, J. Lewis, J. N. Nicholls, P. R. Raithby and M. J. Rosales, J. Chem. Soc., Dalton Trans., 1983, 2311 RSC.
  14. Using a two necked flask fitted with a gas inlet port and a reflux condenser, Ru5C(CO)15(0.020 g, purple, IR νCO CH2Cl2 2067(s) and 2034(m) cm–1) in CH2Cl2(20 m) was reacted with H2S at ca. 20 °C for 5 minutes to afford HRu5C(CO)14(µ-SH)(yellow, IR νCO CH2Cl2 2105(w), 2080(m), 2059(s), 2036(w), 2019(w), 2009(w) and 1963(vw) cm–1) as described in ref. 9. IR spectroscopy and thin layer chromatography showed that conversion takes place quantitatively. Nitrogen was bubbled through this HRu5C(CO)14(µ-SH) solution in order to remove any unreacted H2S. The solution was then heated to reflux (ca. 42 °C) and a steady stream of CO was passed through it for 25 minutes during which time the colour reverted back to the original purple. IR spectroscopy indicated quantitative conversion to Ru5C(CO)15 had taken place and mass spectroscopy was used to confirm the presence of sulfur [m/z 256 (rel. int. 20%) S8, 224 (3%) S7, 192 (11%) S6, 160 (14%) S5, 128 (85%) S4, 96 (20%) S3, 64 (7%) S2]. Mass spectrometry of HRu5C(CO)14(µ-SH) did not show the presence of elemental sulfur. The process was repeated several times and the reaction traced by IR spectroscopy.
  15. A. J. Arce, Y. de Sanctis, A. Karam and A. J. Deeming, Angew. Chem., Int. Ed. Engl., 1994, 33, 1381 CrossRef.
  16. C. R. Eady, B. F. G. Johnson and J. Lewis, J. Chem. Soc., Chem. Commun., 1976, 302 RSC.
  17. C.-M. T. Hayward and J. R. Shapley, Inorg. Chem., 1982, 21, 3816 CrossRef CAS.
  18. B. F. G. Johnson, R. A. Kamarudin, F. J. Lahoz, J. Lewis and P. R. Raithby, J. Chem. Soc., Dalton Trans., 1988, 1205 RSC.
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