Homogeneous Catalysis of Hydrogen Isotope Exchange between D2 and Ethanol by Chlorotris(triphenylphosphine)rhodium(I). I. in Benzene–Ethanol
- 15 June 1974
- journal article
- Published by Canadian Science Publishing in Canadian Journal of Chemistry
- Vol. 52 (12) , 2216-2225
- https://doi.org/10.1139/v74-321
Abstract
The kinetics and mechanism of D2–C2H5OH exchange catalyzed by chlorotris(triphenylphosphine)rhodium(I) have been studied in 50 volume percent benzene-ethanol. In this mixed solvent, the rate of exchange was low and was limited by the rate of transfer of deuterium from dideuteridochlorotris(triphenylphosphine)rhodium(III) to the solvent, and not by the rate of activation of D2. The activation energy for the overall process was relatively low, 35 kJ mol−1. In addition, new data have been presented for the catalysis of H2–D2 exchange in benzene by RhCl(PPh3)3. Analysis of the apparent HD:D2 isotope effect that is observed during D2–C2–H5OH exchange suggests that this effect originates with the relative stabilities of the D2, HD, and H2 adducts with RhCl(PPh3)3, or by control of the HD and H2 product distribution by the H2–D2 equilibration reaction.Keywords
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