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

研究成果: Contribution to journalArticle査読

1 被引用数 (Scopus)

抄録

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.

本文言語英語
ページ(範囲)1400-1412
ページ数13
ジャーナルMolecular Physics
113
12
DOI
出版ステータス出版済み - 6 18 2015
外部発表はい

All Science Journal Classification (ASJC) codes

  • 生物理学
  • 分子生物学
  • 凝縮系物理学
  • 物理化学および理論化学

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