Hydrogen generation from alcohols (α-hydroxy carboxylic acids) and alcohol-ammonia coupling in aqueous media catalysed by water-soluble bipyridine-Cp Ir (Rh or Os) catalyst: A computational mechanism insight

Dan Dan Zhang, Xian Kai Chen, Hui Ling Liu, Xu Ri Huang

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1 Citation (Scopus)

Abstract

Density functional theory (DFT) calculations were performed to elucidate the mechanism of the dehydrogenative oxidation of various primary alcohols (or α-hydroxy carboxylic acids) and the dehydrogenative coupling of alcohols with ammonia catalysed by the same water-soluble Cp Ir complex bearing a 2-pyridonate-based ligand (A-Ir). Another two new catalysts A-Rh and A-Os are computationally designed for the dehydrogenative oxidation of alcohols. The plausible pathway for alcohol dehydrogenation includes three steps: alcohol oxidation to aldehyde (step I); the generation of dihydrogen in the metal coordination sphere (step II); and the liberation of dihydrogen accompanied with the regeneration of active catalyst A (step III). Among them, the step I follows bifunctional concerted double hydrogen transfer mechanism rather than the β-H elimination. For step II, the energy barriers involving the addition of one or two water molecules are higher than in absence of water. Our results also confirm that A-Ir can be applied in the dehydrogenation of various α-hydroxy carboxylic acids by the similar mechanism. Remarkably, A-Ir is also found to be efficient for the coupling reactions of various primary benzyl alcohols with ammonia to afford amides.

Original languageEnglish
Pages (from-to)1400-1412
Number of pages13
JournalMolecular Physics
Volume113
Issue number12
DOIs
Publication statusPublished - Jun 18 2015
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Biophysics
  • Molecular Biology
  • Condensed Matter Physics
  • Physical and Theoretical Chemistry

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