View PDF Version
 
DOI: 10.1039/A800937F (Paper) Reference Section for: J. Chem. Soc., Perkin Trans. 2, 1998, 1147-1152

Photoinduced configurational instability at iron in the aminocarbene complexes [(η5-C5H5)Fe(CO)(L){[double bond, length half m-dash]C(NHR2)(CH2R1)}]+BF4–

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

Stephen G. Davies, Simon Jones, Michael R. Metzler, Kazuo Yanada and Reiko Yanada

Abstract

Photoinduced epimerisation of chiral iron aminocarbene complexes of the type [(η5-C5H5)Fe(CO)(L){[double bond, length half m-dash]C(NHR2)(CH2R1)}]+BF4– [L = PPh3, P([hair space]p-tolyl)3; R1 = H, Me; R2 = CH2Ph, CH(Me)Ph] has been observed in 10% H2O–MeOH, MeOH, EtOH, THF and CH2Cl2 at room temperature. Exchange experiments have unambiguously established that reversible phosphine ligand (L) dissociation rather than reversible loss of the carbon monoxide ligand is the only mechanism operating.

References

  1. S. G. Davies, A. J. Edwards, S. Jones, M. R. Metzler, K. Yanada and R. Yanada, J. Chem. Soc., Dalton Trans., 1998, in the press Search PubMed.
  2. A. Davison and D. L. Reger, J. Am. Chem. Soc., 1972, 94, 9237 CrossRef CAS.
  3. S. G. Davies, M. R. Metzler, K. Yanada and R. Yanada, J. Chem. Soc., Chem. Commun., 1993, 658 RSC.
  4. A. Campbell and J. Kenyon, J. Chem. Soc., 1946, 25 RSC.
  5. F. Nerdel, H. Goetz and M. Fenske, Annalen der Chemie, 1963, 665, 21 Search PubMed.
  6. G. L. Geoffroy and M. S. Wrighton, Organometallic Photochemistry, Academic Press, New York, 1979 Search PubMed.
  7. (a) C. J. Richards and S. E. Thomas, J. Chem. Soc., Chem. Commun., 1990, 307 RSC; (b) N. W. Alcock, C. J. Richards and S. E. Thomas, Organometallics, 1991, 10, 231 CrossRef CAS.
  8. R. Aumann, Angew. Chem., Int. Ed. Engl., 1988, 27, 1456 CrossRef.
  9. P. Hofmann, L. A. Perez-Moya, O. Steigelmann and J. Riede, Organometallics, 1992, 11, 1167 CrossRef CAS.
  10. G. L. Geoffroy and S. L. Bassner, Adv. Organomet. Chem., 1988, 28, 1 CAS.
  11. (a) J. M. Brown and K. Mertis, J. Chem. Soc., Perkin Trans. 2, 1973, 1993 RSC; (b) J. M. Brown, J. A. Conneely and K. Mertis, J. Chem. Soc., Perkin Trans. 2, 1974, 905 RSC.
  12. H. C. Choi and E. L. Muetterties, J. Am. Chem. Soc., 1982, 104, 153 CrossRef CAS.
  13. T. T. Wenzel and R. G. Bergman, J. Am. Chem. Soc., 1986, 108, 4856 CrossRef CAS.
  14. J. P. Bibler and A. Wojcicki, Inorg. Chem., 1966, 5, 889 CrossRef CAS.
  15. M. Green and D. J. Westlake, J. Chem. Soc. A, 1971, 367 RSC.
  16. S. C. Case-Green, J. F. Costello, S. G. Davies, N. Heaton, C. J. R. Hedgecock, V. M. Humphreys, M. R. Metzler and J. C. Prime, J. Chem. Soc., Perkin Trans. 1, 1994, 933 RSC.
  17. After this work was complete the neutral complex [(C5H5)Mn(CO)(PPh3){[double bond, length as m-dash]C(OMe)Et}] was reported to undergo relatively slow (33% in 6.75 days) phosphine exchange in the presence of P(p-tolyl)3. An associative mechanism was indicated for this apparently thermal process: C. Kelley, N. Lugan, M. R. Terry, G. L. Geoffroy, B. S. Haggerty and A. L. Rheingold, J. Am. Chem. Soc., 1992, 114, 6735 Search PubMed.
  18. D. F. Shriver, The Manipulation of Air-Sensitive Compounds, McGraw-Hill, New York, 1969 Search PubMed.
  19. (a) A. C. Cope, C. R. Ganellin, H. W. Johnson, Jr., T. V. Van Auken and H. J. S. Winkler, J. Am. Chem. Soc., 1963, 85, 3276 CrossRef CAS; (b) D. Parker and R. J. Taylor, Tetrahedron, 1987, 43, 5451 CrossRef CAS.
  20. M. L. H. Green, L. C. Mitchard and M. G. Swanick, J. Chem. Soc. A, 1971, 794 RSC.
  21. F. Kroehnke, Chem. Ber., 1935, 68B, 1177 Search PubMed.
Click here to see how this site uses Cookies. View our privacy policy here.