Metal-ligand cooperation in H2 production and H2O decomposition on a Ru(II) PNN complex

The role of ligand dearomatization- aromatization

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Abstract

(Chemical Equation Presented) The molecular mechanism for H2 production and H2O decomposition on an aromatic Ru(II) PNN complex developed by Milstein and co-workers has been elucidated by detailed density functional theory calculations. The rate-determining step is heterolytic coupling of the hydride with a proton transferred from the PNN ligand, which leads to the formation of H2. The metal center and the PNN ligand, which can be dearomatized and aromatized again, play active and synergistic roles in H2 production and the succeeding H2O decomposition. Formation of the cis-dihydroxo complex as the main final product is a result of thermodynamic control.

Original languageEnglish
Pages (from-to)13584-13585
Number of pages2
JournalJournal of the American Chemical Society
Volume131
Issue number38
DOIs
Publication statusPublished - Oct 13 2009

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Aromatization
Metals
Ligands
Decomposition
Thermodynamics
Hydrides
Density functional theory
Protons

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

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title = "Metal-ligand cooperation in H2 production and H2O decomposition on a Ru(II) PNN complex: The role of ligand dearomatization- aromatization",
abstract = "(Chemical Equation Presented) The molecular mechanism for H2 production and H2O decomposition on an aromatic Ru(II) PNN complex developed by Milstein and co-workers has been elucidated by detailed density functional theory calculations. The rate-determining step is heterolytic coupling of the hydride with a proton transferred from the PNN ligand, which leads to the formation of H2. The metal center and the PNN ligand, which can be dearomatized and aromatized again, play active and synergistic roles in H2 production and the succeeding H2O decomposition. Formation of the cis-dihydroxo complex as the main final product is a result of thermodynamic control.",
author = "Jun Li and Yoshihito Shiota and Kazunari Yoshizawa",
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T1 - Metal-ligand cooperation in H2 production and H2O decomposition on a Ru(II) PNN complex

T2 - The role of ligand dearomatization- aromatization

AU - Li, Jun

AU - Shiota, Yoshihito

AU - Yoshizawa, Kazunari

PY - 2009/10/13

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AB - (Chemical Equation Presented) The molecular mechanism for H2 production and H2O decomposition on an aromatic Ru(II) PNN complex developed by Milstein and co-workers has been elucidated by detailed density functional theory calculations. The rate-determining step is heterolytic coupling of the hydride with a proton transferred from the PNN ligand, which leads to the formation of H2. The metal center and the PNN ligand, which can be dearomatized and aromatized again, play active and synergistic roles in H2 production and the succeeding H2O decomposition. Formation of the cis-dihydroxo complex as the main final product is a result of thermodynamic control.

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