Synthesis and Reaction Chemistry of Some Ferrocene-Containing Chelate Ligands with Dirhodium Acetate: X-ray Crystal Structure of $(\eta^1-(S,R)-CPFA)_2Rh_2(OAc)_4$

  • Kim, Eun-Jin (Department of Industrual Chemistry, Kyungpook National University) ;
  • Kim, Tae-Jeong (Department of Industrual Chemistry, Kyungpook National University)
  • Published : 1994.11.20

Abstract

New ferrocene-based chelate amines, $Fe[C_5H_4CH(Me)NMe_2]_2\;(3), \;Fe[C_5H-3(CH(Me)NMe_2)(PPh_2)-1,2]_2\;(4),\;(C_5H_5)Fe(C_5H_3(CH_2NMe_2)(CH(CN)NMe_2-1,2)\;(6),\;and\;(C_5H_5)Fe(C_5H_3(CH_2NMe_2)(CH(Me)NMe_2-1,2)$ (7) have been prepared. The reaction and the coordination chemistry of 4 and other related compounds (S,R)-(1-N,N-dimethylaminoethyl)-2-dicyclohexylphosphino)ferrocene (CPFA) and 1,1'-bis-(diphenylphosphino)ferrocene (BPPF) with $Rh_2(OAc)_4(MeOH)_2$ were investigated. The reaction of the chiral ligand (S,R)-CPFA forms a complex of the type (${\eta}^1$-(S,R)-CPFA-P)$_2Rh_2(OAc)_4$ (8) in which the ligand is coordinated to both rhodium centers in a monodentate fashion through phosphorus. In contrast, the bisphosphine analogues such as BPPF and 4 afford chelate complexes of the type (${\eta}^2-PP)Rh_2(OAc)_4$ (9 & 10) where both ligands act as a chelate bidentate to a single rhodium atom. All these complexes were characterized by microanalytical and spectroscopic techniques. In one case, the structure of 8 was determined by X-ray crystallography. Crystals are monoclinic, space group C2 (No. 5), with a=26.389 (3), b=12.942 (1), c=11.825 (1) A, ${\beta}$=111.22(1)$^{\circ}$, V=3964.7 (8) $A^3$, Z=4, and $D_{calc}$=1.58 g $cm^{-3}$. Two Rh(II) centers are bridged by four $AcO^-$ groups in the ${\eta}^1$ : ${\eta}^1$ mode across a Rh-Rh single bond, and octahedral coordination at Rh(1) and Rh(1') is completed by axially coordinating (S,R)-CPFA and a briding $AcO^-$, respectively.

Keywords

References

  1. Inorg. Chem. v.26 Aquiso, M. A. S.;Macartney, D. H.
  2. Prog. Inorg. Chem. v.29 Felthouse, T. R.
  3. Coord. Chem. Rev. v.50 Boyar, E. B.;Robinson, S. D.
  4. Multiple Bonds Between Metal Atoms Cotton, F. A.;Walton, R. A.
  5. Cancer. Res. v.36 Howard, R. A.;Spring, T. G.;Bear, J. L.
  6. J. Inorg. Nucl. Chem. v.33 Bear, J. L.;Kitchens, J.;Willcott, M. R.
  7. Inorg. Chem. v.27 Cotton, F. A.;Barcelo, F.;Lahuerta, P.;Lluser, R.;Paya, J.;Ubeda, M. A.
  8. J. Organomet. Chem. v.373 Lahuerta, P.;Paya, J.;Peris, E.;Pellinghelli, M. A.;Tiripicchio, A.
  9. Inorg. Chem. v.31 Lahuerta, P.;Paya, J.;Bianchi, A.
  10. Inorg. Chem. v.31 Lahuerta, P.;Paya, J.;Pellinghelli, M. A.;Tiripicchio, A.
  11. Inorg. Chem. v.31 Lahuerta, P.;Paya, J.;Solans, X.;Ubeda, M. A.
  12. J. Organomet. Chem. v.455 Lahuerta, P.;Peris, E.;Udeda, M. A.;Gracia-Granda, S.;Gomez-Beltran, F.;Diaz, M. R.
  13. J. Organomet. Chem. v.443 Lahuerta, P.;Paya, J.;Garcia-Granda, S.;Gomez-Beltran, F.;Anillo, A.
  14. Bull. Korean Chem. Soc. v.10 Kim, T. J.;Lee, K. C.
  15. Chem. Rev. v.86 Doyle, M. P.
  16. Top. Curr. Chem. v.137 Mass, G.
  17. Synthesis Hubert, A. J.;Noels, A. F.;Teyssie, P.
  18. Org. Chem. v.45 Anciaux, A. J.;Hubert, A. J.;Noel, A. F.;Petinot, N.;Teyssie, P. J.
  19. Organometallics v.3 Doyle, M. P.;Dorow, R. L.;Buhro, W. E.;Griffine, J. H.;Tamblyn, W. H.;Trudell, M. L.
  20. Acc. Chem. Res. v.19 Doyle, M. P.
  21. Purification of Laboratory Chemicals Perrin, D. D.;Armarego, W. L. F.
  22. J. Organomet. Chem. v.27 Bishop, J. J.;Davison, A.;Katcher, M. L.;Lichtenberg, D. W.;Merril, R. E.;Smart, J. C.
  23. Bull. Korean Chem. v.13 Kim, T. J.;Kim, Y. H.;Kim, H. S.;Shim, S. C.;Kwak, Y. W.;Cha, J. S.;Lee, H. S.;Uhm, J. K.;Byun, S. I.
  24. J. Am. Chem. Soc. v.92 Marquarding, D.;Klusacck, H.;Gokel, G.;Hoffman, P.;Ugi, I.
  25. J. Chem. Educ. v.49 Gokel, G.;Ugi, I.
  26. J. Org. Chem. v.22 Hauser, C. R.;Lindsay, J. K.
  27. Bull. Chem. Soc. Jpn. v.53 Hayashi, T.;Mise, T.;Fukushima, M.;Katagoni, M.;Nagashima, M.;Hamada, Y.;Matsumoto, A.;Kawakami, S.;Konishi, M.;Kumada, M.
  28. J. Organomet. Chem. v.412 Balavoine, G. G. A.;Doisneau, G.;Fillebeen-Khan, T.
  29. Inorg. Synth. v.13 Rempel, G. A.;Legzdins, P.;Smith, H.;Wilkinson, G.
  30. J. Organometallics v.2 Cullen, W. R.;Einstein, F. W. B.;Jones, T.;Kim, T.
  31. Inorg. Chem. v.32 Crawford, C. A.;Matonic, J. H.;Streib, W. E.;Huffman, J. C.;Dunbar, K. R.;Chirstou, G. C.
  32. J. Organomet. Chem. v.426 Kim, T. J.;Kwon, S. C.;Kim, Y. H.;Heo, N. H.
  33. J. Organomet. Chem. v.373 Hor, T. S. A.;Phang, L. T.
  34. J. Organomet. Chem. v.408 Morrison, E. C.;Tocher, D. A.