Metal-ligand cooperation in H2 production and H2O decomposition on a Ru(II) PNN complex: The role of ligand dearomatization- aromatization

Jun Li; Yoshihito Shiota; Kazunari Yoshizawa

doi:10.1021/ja905073s

Metal-ligand cooperation in H₂ production and H₂O decomposition on a Ru(II) PNN complex: The role of ligand dearomatization- aromatization

Jun Li, Yoshihito Shiota, Kazunari Yoshizawa

Department of Fundamental Organic Chemistry

Research output: Contribution to journal › Article › peer-review

90 Citations (Scopus)

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 language	English
Pages (from-to)	13584-13585
Number of pages	2
Journal	Journal of the American Chemical Society
Volume	131
Issue number	38
DOIs	https://doi.org/10.1021/ja905073s
Publication status	Published - 2009

All Science Journal Classification (ASJC) codes

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

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10.1021/ja905073s

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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.",

author = "Jun Li and Yoshihito Shiota and Kazunari Yoshizawa",

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AU - Yoshizawa, Kazunari

PY - 2009

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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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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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