Novel low-valent zirconium porphyrin complexes: syntheses, characterization and X-ray crystal structures of (η5-cyclopentadienyl)zirconium tetraphenylporphyrin and (η2-diphenylacetylene)zirconium octaethylporphyrin

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

Hee-Joon Kim, Sungkyung Jung, You-Moon Jeon and Kimoon Kim


Abstract

Reactions of (por)ZrCl2 [por = octaethylporphyrinato (oep) or tetraphenylporphyrinato (tpp) dianion] with TlCp and diphenylacetylene in the presence of Na/Hg or Mg produce novel low-valent zirconium porphyrin complexes (por)Zr(η5-Cp) 1 and (por)Zr(η2-PhC[triple bond, length half m-dash]CPh) 2, respectively; spectroscopic and/or structural data for 1 and 2 are consistent with a formalism in which 1 is a resonance hybrid of a zirconium(III) metal-centered radical and a zirconium(IV) porphyrin radical anion while 2 is a zirconium(II) complex stabilized by a four-electron-donor alkyne ligand.


References

  1. R. D. Broene and S. L. Buchwald, Science, 1993, 261, 1696; E. Negishi and T. Takahashi, Acc. Chem. Res., 1994, 27, 124 CrossRef CAS; S. L. Buchwald and R. B. Nielsen, Chem. Rev., 1988, 88, 1047 CrossRef; P. Binger and S. Podubrin, in Comprehensive Organometallic Chemistry II, ed. M. F. Lappert, Elsevier, New York, 1995, vol 4, p. 439 Search PubMed.
  2. E. Negishi, S. J. Holmes, J. M. Tour, J. A. Miller, F. E. Cederbaum, D. R. Swanson and T. Takahashi, J. Am. Chem. Soc., 1989, 111, 3336 CrossRef CAS; M. Jensen and T. Livinghouse, J. Am. Chem. Soc., 1989, 111, 4495 CrossRef CAS; W. A. Nugent and D. F. Taber, J. Am. Chem. Soc., 1989, 111, 6435 CrossRef CAS.
  3. (a) H. Brand and J. Arnold, J. Am. Chem. Soc., 1992, 114, 2266 CrossRef CAS; (b) J. Arnold, S. E. Johnson, C. B. Knobler and M. F. Hawthorne, J. Am. Chem. Soc., 1992, 114, 3996 CrossRef CAS; (c) H. Brand and J. Arnold, Organometallics, 1993, 12, 3655 CrossRef CAS; (d) H. Brand, J. A. Capriotti and J. Arnold, Organometallics, 1994, 13, 4469 CrossRef CAS; (e) H. Brand and J. Arnold, Angew. Chem., Int. Ed. Engl., 1994, 33, 95 CrossRef.
  4. H.-J. Kim, D. Whang, K. Kim and Y. Do, Inorg. Chem., 1993, 32, 360 CrossRef CAS; H.-J. Kim, D. Whang, Y. Do and K. Kim, Chem. Lett., 1993, 807; S. Ryu, D. Whang, H.-J. Kim, K. Kim, M. Yoshida, K. Hashimoto and K. Tatsumi, Inorg. Chem., in press Search PubMed.
  5. (a) K. Shibata, T. Aida and S. Inoue, Tetrahedron Lett., 1992, 33, 1077 CrossRef CAS; (b) K. Shibata, T. Aida and S. Inoue, Chem. Lett., 1992, 1173 CAS.
  6. H.-J. Kim, S. Jung, D. Whang, Y.-M. Jeon and K. Kim, manuscript in preparation.
  7. J. Arnold and C. G. Hoffman, J. Am. Chem. Soc., 1990, 112, 8620 CrossRef CAS.
  8. L. K. Woo, J. A. Hays, R. A. Jacobson and C. L. Day, Organometallics, 1991, 10, 2102 CrossRef CAS; L. K. Woo, J. A. Hays, V. G. Young, C. L. Day, C. Caron, F. D'Souza and K. M. Kadish, Inorg. Chem., 1993, 32, 4186 CrossRef CAS.
  9. T. Takahashi, D. R. Swanson and E. Negishi, Chem. Lett., 1987, 623 CAS.
  10. J. L. Templeton, Adv. Organomet. Chem., 1989, 29, 1 CAS.
Click here to see how this site uses Cookies. View our privacy policy here.