View PDF Version
 
DOI: 10.1039/A707435B (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1998, 1403-1410

Rhodium carbonyl complexes containing pyridine; crystal structure of an unusual octahedral rhodium(I) complex [Rh2(µ-CO)3Cl2(py)4]

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

Brian T. Heaton, Chacko Jacob and Jeyagowry T. Sampanthar

Abstract

The products resulting from the progressive addition of pyridine (py) to a solution of [Rh2(µ-Cl)2(CO)4] 1 have been found to depend both upon the solvent and the atmosphere (CO or N2). In CH2Cl2 under N2, cis-[Rh(CO)2Cl(py)] 2, [Rh(CO)2Cl(py)2] 3 and [Rh2(µ-CO)3Cl2(py)4] 4 were obtained successively; under CO, 4 was converted into 3 and under N2 disproportionation of 4 slowly occurred to give 3 and trans-[Rh(CO)Cl(py)2] 5 which reacted with CO to give 3. In more polar solvents (thf or MeOH), 1 reacted under N2 to give the lightly solvent-stabilised complex [Rh(CO)2Cl(solv)] 6 (solv = thf a or MeOH b) and, in the presence of AgClO4, cis-[Rh(CO)2(solv)2]+ 7 (solv = thf a or MeOH b); additionally, when solv = MeOH there was spectroscopic evidence for the formation of [Rh2(µ-CO)x(MeOH)y]2+ 8 (x = 2, y = 4 or x = 3, y = 6) which reacted with CO to give [Rh(CO)2(MeOH)2]+. Complex 7 reacted with py to give successively cis-[Rh(CO)2(py)2]+ 9 and [Rh(CO)(py)3]+ 10; under CO 10 was converted into 9. The stereochemistry of all the above complexes has been established through a combination of IR and multinuclear (13C, 15N, 103Rh) NMR measurements and X-ray crystallography for 2 and 4. Analogous reactions have been carried out using trans-[Rh2(µ-Cl)2(CO)2(CxHy)2] 11 (CxHy = C2H4 a or C8H14 b) under a nitrogen atmosphere and spectroscopic measurements on the reaction of 11a with pyridine were consistent with the successive formation of [Rh2(µ-Cl)2(CO)2(C2H4)2(py)2] 12, which lost ethylene and rearranged to give [Rh2(µ-CO)2Cl2(py)2] 13. Reaction of 11b with pyridine gave immediately trans-[Rh2(µ-Cl)2(CO)2(py)2] 14 and both 13 and 14 further reacted with pyridine to give 5.

References

  1. B. T. Heaton, C. Jacob, G. K. Monks, M. B. Hursthouse, I. Ghatak, R. G. Sommerville, W. Heggie, P. R. Page and I. Villax, J. Chem. Soc., Dalton Trans., 1996, 61 RSC and refs. therein.
  2. B. T. Heaton, J. A. Iggo, C. Jacob, J. Nadarajah, M. A. Fontaine, R. Messere and A. F. Noels, J. Chem. Soc., Dalton Trans., 1994, 2875 RSC and refs. therein.
  3. A. J. Pardey and P. C. Ford, J. Mol. Catal., 1989, 53, 247 CrossRef CAS.
  4. K. Kaneda, M. Hiraki, K. Sano, T. Imanaka and S. Teranishi, J. Mol. Catal., 1980, 9, 227 CrossRef CAS.
  5. G. Fachinetti, G. Focki and T. Funaioli, Inorg. Chem., 1994, 33, 1719 CrossRef CAS.
  6. W. Hieber, H. Heusinger and O. Vohler, Chem. Ber., 1957, 90, 2425 CAS.
  7. P. S. Hall, G. E. Jackson, J. R. Moss, D. A. Thornton, P. F. M. Verhoeven and G. M. Watkins, Spectrosc. Lett., 1993, 26, 1247.
  8. A. J. Pribula and R. S. Drago, J. Am. Chem. Soc., 1976, 98, 2784 CrossRef CAS.
  9. D. N. Lawson and G. Wilkinson, J. Chem. Soc., 1965, 1900 RSC.
  10. R. Poilblanc, J. Organomet. Chem., 1975, 94, 241 CrossRef CAS.
  11. G. A. Morris and R. Freeman, J. Am. Chem. Soc., 1979, 101, 760 CrossRef CAS.
  12. G. Fachinetti, T. Funaioli and P. F. Zanazzi, J. Organomet. Chem., 1993, 460, C34 CrossRef CAS.
  13. F. Shafiq and R. Eisenberg, Inorg. Chem., 1993, 32, 3287 CrossRef CAS.
  14. J. P. Farr, M. M. Olmstead and A. L. Balch, J. Am. Chem. Soc., 1980, 102, 6654 CrossRef CAS.
  15. F. Shafiq and R. Eisenberg, Abstr. Papers Am. Chem. Soc. Meeting, 1992, 204, 427 Search PubMed.
  16. B. T. Heaton, C. Jacob, W. Heggie, P. R. Page and I. Villax, Magn. Reson. Chem., 1991, 29, S21 CAS.
  17. R. Cramer, Inorg. Synth., 1974, 15, 14 CAS.
  18. A. Ent and A. L. Onderdelinden, Inorg. Synth., 1973, 14, 93.
  19. J. A. McCleverty and G. Wilkinson, Inorg. Synth., 1966, 8, 211 CAS.
  20. A. C. T. North, D. C. Phillips and F. S. Mathews, Acta Crystallogr., Sect. A, 24, 351 Search PubMed.
  21. TEXSAN-TEXRAY, Structure Analysis Package, Molecular Structure Corporation, Houston, TX, 1989.
  22. D. T. Cromer and J. T. Waber, International Tables for X-Ray Crystallography, Kynoch Press, Birmingham, 1974, vol. 4, Table 2.2A Search PubMed.
  23. C. K. Johnson, ORTEP, Report ORNL-5138, Oak Ridge National Laboratory, Oak Ridge, TN, 1976.
Click here to see how this site uses Cookies. View our privacy policy here.