Thiobenzamidato and thiobenzoato complexes of ruthenium, osmium and iridium

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Stephen D. Robinson, Arvind Sahajpal and Derek A. Tocher


Abstract

Thiobenzamide reacted with the complexes [MCl2(PPh3)3], [MH(X)(CO)(PPh3)3] (M = Ru or Os, X = H or Cl) and mer-[IrH3(PPh3)3] in boiling toluene to afford the products [M{S(NH)CPh}2(PPh3)2], [MX{S(NH)CPh}(CO)(PPh3)2] and [IrH2{S(NH)CPh}(PPh3)2] respectively. The crystal structure of [Os{S(NH)CPh}2(PPh3)2] confirms the expected bis(N,S-chelate) formulation and has established the presence of cis-phosphorus, cis-nitrogen and trans-sulfur donor atom pairs within a highly distorted octahedral co-ordination sphere. Thiobenzoic acid reacted with [MCl2(PPh3)3] and [MH(X)(CO)(PPh3)3] under similar conditions to yield [M{S(O)CPh}2(PPh3)2] and [M{S(O)CPh}2(CO)(PPh3)2] respectively. The reactions of thiobenzoic acid with mer-[IrH3(PPh3)3] under conditions of increasing severity give [IrH2{S(O)CPh}(PPh3)3], [IrH{S(O)CPh}2(PPh3)2] and [Ir{S(O)CPh}3(PPh3)2] the last two of which on carbonylation afford [IrH{S(O)CPh}2(CO)(PPh3)2] and [Ir{S(O)CPh}3(CO)(PPh3)2] respectively. The crystal structure of [IrH{S(O)CPh}2(PPh3)2] has established the presence of trans phosphorus and trans sulfur donor atom pairs, with the η1- and η2-thiobenzoate ligands sharing a meridional set of three co-ordination sites. However, the NMR spectra of this complex show two high-field 1H triplets and two 31P-{1H} singlets. Possible explanations for this anomalous NMR behaviour, which is also found for the corresponding thioacetate, are advanced.


References

  1. Part 47, S. D. Robinson, A. Sahajpal and D. A. Tocher, J. Chem. Soc., Dalton Trans., 1995, 3497 Search PubMed.
  2. M. B. Hursthouse, M. A. Mazid, S. D. Robinson and A. Sahajpal, J. Chem. Soc., Dalton Trans., 1993, 2835 RSC.
  3. M. B. Hursthouse, M. A. Mazid, S. D. Robinson and A. Sahajpal, J. Chem. Soc., Dalton Trans., 1994, 3615 RSC.
  4. S. D. Robinson and M. F. Uttley, J. Chem. Soc., Dalton Trans., 1973, 1912 RSC.
  5. A. Dobson, S. D. Robinson and M. F. Uttley, J. Chem. Soc., Dalton Trans., 1975, 370 RSC.
  6. G. M. Sheldrick, SHELXL 93, University of Göttingen, 1993.
  7. S. R. Fletcher and A. C. Skapski, J. Chem. Soc., Dalton Trans., 1972, 635 RSC.
  8. R. O. Gould, T. A. Stephenson and M. A. Thomson, J. Chem. Soc., Dalton Trans., 1978, 769 RSC.
  9. J. D. Gilbert and G. Wilkinson, J. Chem. Soc. A, 1969, 1749 RSC.
  10. P. B. Critchlow and S. D. Robinson, Inorg. Chem., 1978, 17, 1902 CrossRef CAS.
  11. P. M. Boyer, C. P. Roy, J. M. Bielski and J. S. Merola, Inorg. Chim. Acta, 1996, 245, 7 CrossRef CAS and refs. therein.
  12. J. C. Lee, E. Peris, A. L. Rheingold and R. H. Crabtree, J. Am. Chem. Soc., 1994, 116, 11014 CrossRef.
  13. J. C. Lee, A. L. Rheingold, B. Muller, P. S. Pregosin and R. H. Crabtree, J. Chem. Soc., Chem. Commun., 1994, 1021 RSC.
  14. E. Peris, J. C. Lee, J. R. Rambo, O. Eisenstein and R. H. Crabtree, J. Am. Chem. Soc., 1995, 117, 3485 CrossRef CAS.
  15. A. J. Lough, S. Park, R. Ramachandran and R. H. Morris, J. Am. Chem. Soc., 1994, 116, 8356 CrossRef CAS.
  16. S. J. Park, R. Ramachandran, A. J. Lough and R. H. Morris, J. Chem. Soc., Chem. Commun., 1994, 2201 RSC.
  17. D. Milstein, J. C. Calabrese and I. D. Williams, J. Am. Chem. Soc., 1986, 108, 6387 CrossRef CAS.
  18. R. C. Stevens, R. Bau, D. Milstein, O. Blum and T. F. Koetzle, J. Chem. Soc., Dalton Trans., 1990, 1429 RSC.
  19. S. A. Fairhurst, R. A. Henderson, D. L. Hughes, S. K. Ibrahim and C. J. Pickett, J. Chem. Soc., Chem. Commun., 1995, 1569 RSC.
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