Evidence for a 1,2-shift mechanism for the rearrangement of σ-cyclopentadienyl compounds of iron, ruthenium, and copper
- 1 January 1970
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc. A
- p. 1318-1323
- https://doi.org/10.1039/j19700001318
Abstract
The low-temperature 1H n.m.r.spectra of the new compounds (π-C5H5)Ru(CO)2(σ-C5H4R)(R = H or Me) have been studied and those of (π-C5H5)Fe(CO)2(σ-C5H5) and (σ-C5H5)CuPEt3 have been re-examined. Satellite lines due to coupling to 13C were observed in the spectra of the compounds (π-C5H5)M(CO)2(σ-C5H5)(M = Fe or Ru) by spectrum accumulation at low temperature. The results indicate that in each of the three compounds with an unsubstituted σ-cyclopentadienyl ring the metal migrates round this ring by a sequence of 1,2-shifts. For the compounds (π-C5H5)M(CO)2(σ-C5H5)(M = Fe or Ru) the activation energies for this process were found to be 8·5 ± 0·8 and 9·6 ± 1·0 kcal. mole–1 respectively. Migration of the metal atom round the σ-bonded ring also occurs in (π-C5H5)Ru(CO)2(σ-C5H4Me) and this is discussed.Keywords
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