Comparative DFT Analysis of Ligand and Solvent Effects on the Mechanism of H2 Activation in Water Mediated by Half-Sandwich Complexes [Cp′Ru(PTA)2Cl] (Cp′ = C5
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- 作者：Gbor Kovcs ; Andrea Rossin ; Luca Gonsalvi ; Agust Lleds ; Maurizio Peruzzini
- 刊名：Organometallics
- 出版年：2010
- 出版时间：November 8, 2010
- 年：2010
- 卷：29
- 期：21
- 页码：5121-5131
- 全文大小：1089K
- 年卷期：v.29,no.21(November 8, 2010)
- ISSN：1520-6041
文摘
The activation of hydrogen by complexes [Cp′Ru(PTA)2Cl] (Cp′ = C5H5, C5Me5; PTA = 1,3,5-triaza-7-phosphaadamantane) in water was investigated in a comparative DFT study carried out using a discrete + continuum model based on a four-water-molecule cluster. As a starting point were chosen the η2-H2 dihydrogen complexes [Cp′Ru(PTA)2(η2-H2)]+ (1H2), which are formed initially upon reaction of the chloride precursors with hydrogen gas. A rationale for the experimental data, showing that the monohydrido complex [CpRu(PTA){PTA(H)}H]+ (4a) and the dihydrido complex [Cp*Ru(PTA)2(H)2]Cl (3b) are the stable products for the two systems, is proposed, together with an in-depth analysis of both ligand and solvent effects in the stability of the different species, leading to more general mechanistic implications for metal-mediated hydrogen activation in water.