Reactions of diethylamine and ethylene catalyzed by Pt II or Pt 0 : transalkylation vs. hydroamination
Résumé
PtBr2/nBu4PBr (without solvent) or K2PtCl4/NaBr (in water), previously shown to efficiently catalyze the hydroamination of ethylene by aniline, are poor catalysts for the hydroamination of ethylene by diethylamine. A DFT study on the hydroamination mechanism indicates that the energetic span of the C2H4/Et2NH catalytic cycle is close to that of the C2H4/PhNH2 cycle. The poor performance is attributed to rapid catalyst degradation with reduction to metallic platinum. The produced Pt 0 , on the other hand, catalyzes a transalkylation process, partially transforming Et2NH into Et3N, EtNH2, and NH3. The latter process is inhibited by C2H4. Mechanistic considerations on the Pt 0catalyzed transalkylation process are presented.
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