View PDF Version
 
DOI: 10.1039/A702935G (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1997, 2931-2936

Synthesis and characterisation of rhenium dithiocarbamate complexes. Crystal structures of [ReO{O(OH)C6H4}(S2CNEt 2)2], [Re{PPh2(C6H4S-2)}2 (S2CNEt2)]·Me2CO and [ReO{PPh(C6H4S-2)2}(S2 CNEt2)]

(Note: The full text of this document is currently only available in the PDF Version )

Jonathan R. Dilworth, D. Vaughan Griffiths, Suzanne J. Parrott and Yifan Zheng

Abstract

The reaction of [Re2O3(S2CNEt2)4] with catechol in acetone yielded the dark orange complex [ReO{O(OH)C6H4}(S2CNEt 2)2] 1. The crystal structure shows a distorted-octahedral geometry with the oxo group trans to the monodentate catecholate ligand. The Re–O (catechol) bond length is typical of a Re–O single bond and implies little trans influence of the oxo ligand. Reaction of [Re2O3(S2CNEt2)4] with 1,4-dihydroxybenzene yielded the red-brown dimer [{ReO(S2CNEt2)2}2 (C6H4O2-1,4)] 2, in which the dianionic ligand bridges two rhenium centres. With 2-amino-4-methylphenol [ReO(OC6H3NH2-2-Me-4)(S2 CNEt2)2] 3 was obtained containing the ligand co-ordinated in a monodentate mode. Reaction of [Re2O3(S2CNEt2)4] with dithiolate proligands such as ethane-1,2-dithiol yielded [NEt2H2][ReOL2], L = C2H4S2-1,2 4, C6H4S2-1,2 5 or MeC6H3S2-3,4 6, where degradation of the dithiocarbamate ligands to form the diethylammonium counter ion occurs. Reaction of 1 with bidentate phosphines yielded green complexes of the general formula [Re(S2CNEt2)2L][BPh4], where L = Me2PCH2CH2PMe2 7 or Ph2PCH2CH2PPh2 8. These reactions can be contrasted to the inactivity of these phosphine ligands towards [Re2O3(S2CNEt2)4 ]. The reaction of [Re2O3(S2CNEt2)4] with the bidentate phosphinothiolate proligand PPh2(C6H4SH-2) in acetone at room temperature yielded the red-orange rhenium(III) complex [Re{PPh2(C6H4S-2)}2 (S2CNEt2)]·Me2CO 9. The crystal structure revealed a distorted-octahedral geometry. The sulfur donors of the phosphinothiolate ligands adopt a cis configuration. Reaction of [Re2O3(S2CNEt2)4] with the tridentate phosphinothiolate proligand PPh(C6H4SH-2)2 proceeded at room temperature to yield the red rhenium(V) complex [ReO{PPh(C6H4S-2)2}(S2 CNEt2)] 10. Its crystal structure shows a distorted-octahedral geometry. Reaction of [Re2O3(S2CNEt2)4] with SiMe3Cl yielded the new rhenium(V) precursor [ReCl2(S2CNEt2)2][BPh 4] 11 which permits investigation into rhenium dithiocarbamate chemistry without an oxo core.

References

  1. M. Stalteri, S. J. Parrott, J. R. Dilworth, D. V. Griffiths and S. J. Mather, Nucl. Med. Commun., in the press Search PubMed.
  2. C. G. Pierpont and R. M. Buchanan, Coord. Chem. Rev., 1981, 38, 45 CrossRef CAS.
  3. R. H. Heistand II, R. B. Lauffer, E. Fikrig and L. Que, jun., Inorg. Chem., 1982, 21, 676 CrossRef.
  4. M. Kurihara, N. Katoh, T. Kojima, Y. Ishii and Y. Matsuda, Inorg. Chem., 1995, 34, 4888 CrossRef CAS.
  5. E. Block, H. Kang, G. Ofori-Okai and J. Zubieta, Inorg. Chim. Acta, 1990, 166, 155 CrossRef; G. S. White and D. W. Stephan, Inorg. Chem., 1985, 24, 1499 CrossRef CAS; J. R. Dilworth, Y. Zheng, S. Lu and Q. Wu, Transition Met. Chem., 1992, 17, 364 CAS; V. K. Issleib and W. Gans, Z. Anorg. Allg. Chem., 1981, 475, 116 CrossRef; 1982, 491, 163.
  6. J. R. Dilworth, A. J. Hutson, J. S. Lewis, J. R. Miller, Y. Zheng, Q. Chen and J. A. Zubieta, J. Chem. Soc., Dalton Trans., 1996, 1093 RSC.
  7. E. Block, M. Gernon, H. Kang, G. Ofori-Okai and J. Zubieta, Inorg. Chem., 1991, 30, 1736 CrossRef CAS.
  8. T. Osa and T. Kuwana, Electroanal. Chem., 1969, 22, 389 CrossRef CAS.
  9. S. Battacharya and C. G. Pierpont, Inorg. Chem., 1992, 31, 35 CrossRef CAS.
  10. W. A. Nugent and J. M. Mayer, Metal–Ligand Multiple Bonds, Wiley-Interscience, New York, 1988 Search PubMed.
  11. P. J. Blower, J. R. Dilworth, J. P. Hutchinson, T. Nicholson and J. A. Zubieta, J. Chem. Soc., Dalton Trans., 1986, 1339 RSC.
  12. U. Abram and B. Lorentz, Z. Naturforsch, Teil B, 1993, 48, 771 CAS.
  13. J. R. Dilworth, S. A. Ibrahim, S. R. Khan, M. B. Hursthouse and A. A. Karaulov, Polyhedron, 1990, 9, 1323 CrossRef CAS.
  14. M. T. Ahmet, C. Lu, J. R. Dilworth, J. R. Miller, Y. Zheng, D. E. Hibbs, M. B. Hursthouse and K. M. A. Malik, J. Chem. Soc., Dalton Trans., 1995, 3143 RSC.
  15. L. Chang, S. Aizawa, M. J. Heeg and E. Deutsch, Inorg. Chem., 1991, 30, 4920 CrossRef CAS.
  16. J. F. Rowbottom and G. Wilkinson, J. Chem. Soc., Dalton Trans., 1972, 826 RSC.
  17. E. Block, G. Ofori-Okai and J. Zubieta, J. Am. Chem. Soc., 1989, 111, 2327 CrossRef CAS; E. Block, V. Eswarakrishnan, M. Gernon, G. Ofori-Okai, C. Saha, K. Tang and J. Zubieta, J. Am. Chem. Soc., 1989, 111, 658 CrossRef.
  18. G. M. Sheldrick, Acta Crystallogr., Sect. A, 1990, 46, 467 CrossRef.
  19. G. M. Sheldrick, SHELXL 93, Program for Crystal Structure Refinement, University of Göttingen, 1993.
  20. CAD-4 Software, Version 5.0, Enraf-Nonius, Delft, 1989.
  21. L. Zsoluai, ZORTEP, An ellipoid representation program, University of Heidelberg, 1994.
Click here to see how this site uses Cookies. View our privacy policy here.