Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
권호 표지
DOI QR코드

DOI QR Code

Reduction of Alkyl Halides by Homonuclear Bridging Hydride, (μ-H)[(η$^5-MeCp)$Mn(CO)₂]₂-ppn+

  • Published : 1996.03.20
Download PDF
⟨ Previous Next ⟩

Abstract

Alkyl halides were reduced to the corresponding alkanes by the homonuclear bridging hydride, (μ-H)[(η5-MeCp)Mn(CO)2]2-PPN+ in THF at the elevated temperatures (40-60 ℃) under the pseudo first order reaction conditions where excess of alkyl halide was employed under nitrogen atmosphere. The reaction is of overall second order; first order with respect to [bridging hydride] and first order with respect to [alkyl halide] with the activation parameters, ΔH≠=28.93 kcal/mol and ΔS≠=17.95 e.u. The kinetic data, the ESR evidence and the reaction with cyclopropyl canbinyl bromide ensure that two possible reaction pathways are operable in this reaction: (1) concerted mechanism, and (2) single electron transfer pathway are in competition leading to the same product, the corresponding alkane.

Keywords

References

  1. Organometallics v.4 Kao, S. C.;Spillet, C. T.;Ash, C.;Lusk, R.;Park, Y. K.;Darensbourg, M. Y.
  2. Organometallics v.3 Kao, S. C.;Darensbourg, M. Y.
  3. J. Am. Chem. Soc. v.106 Arndt, L.;Delord, T.;Darensbourg, M. Y.
  4. Organometallics v.1 Slater, S. G.;Lusk, R.;Schumann, B.;Darensbourg, M. Y.
  5. J. Chem. Soc. v.92 Nyholm, R. S.;Sabdhu, S. S.
  6. Inorg. Synth. v.19 Butler, I. S.;Coville, N. J.;Cozak, D.(et al.)
  7. Organometallics v.9 Zhuang, Jun-Ming;Batchelor, R. J.;Einstein, F. W. B.;Jones, R. H.;Hader, R.;Sutton, D.
  8. Organometallics v.10 Wieland, S.;Eldik, R. V.
  9. J. Am. Chem. Soc. v.99 Kirtley, S. W.;Andrews, M. A.;Bau, R.;Grynkewich, G. W.;Marks, T . J.;Tipton, D. L.;Whittlesey, B. R.
  10. Bull. Korean Chem. Soc. Park, Y. K.;Lee, Y. G.;Kim, G. S.
  11. J. Am. Chem. Soc. v.104 Darensbourg, M. Y.;Jimenez, P.;Sackett, J. R.;Hankel, J. M.;Kump, R. L.
  12. Inorg. Chem. v.17 Darensbourg, M. Y.;Darensbourg, D. J.;Barros, H. L. C.
  13. Bull, Korean Chem. Soc. v.16 Park, Y. K.;Kim, G. S.;Song, G. O.
  14. Anal. Biochem. v.217 Pou, S.(et al.)
  15. J. Am. Chem. Soc. v.98 Maillard, B.;Forest, D.;Ingold, K. V.
  16. Bull. Korean Chem. Soc. v.11 Park, Y. K.;Kim, S. J.