NMR examination at 45-50°C of a solution containing appropriate isotopically labeled derivatives of Cp2W(H)CH3 shows intramolecular hydrogen exchange between the hydride and methyl ligands of individual molecules, combined at high concentrations with intermolecular hydride exchange. Because of this intermolecular hydride exchange, methane elimination, although intramolecular, appears to be intermolecular at high concentrations. Comparison of the rate of CH4 elimination from Cp2W(H)CH3 with the rate of CD4 elimination from Cp2W(D)CD3 shows an inverse isotope effect of 0.7 at 72.6°C. The reversible formation of a σ complex of methane as an intermediate in the elimination process is the most plausible explanation for the H/CH3 scrambling and for the inverse isotope effect.
|Number of pages||12|
|Journal||Journal of the American Chemical Society|
|Publication status||Published - 1989|
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