Water-Assisted H-H Bond Splitting Mediated by [CpRu(PTA)2Cl] (PTA=1,3,5-triaza-7-phosphaadamantane). A DFT Analysis
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- 作者：Andrea Rossin ; Luca Gonsalvi ; Andrew D. Phillips ; Olivier Maresca ; Agustí ; Lledó ; s ; Maurizio Peruzzini
- 刊名：Organometallics
- 出版年：2007
- 出版时间：July 2, 2007
- 年：2007
- 卷：26
- 期：14
- 页码：3289 - 3296
- 全文大小：439K
- 年卷期：v.26,no.14(July 2, 2007)
- ISSN：1520-6041
文摘
A DFT study using a "discrete-continuum" modeling of the reaction medium, employed to unravel therole of water in the activation of dihydrogen by [CpRu(PTA)2Cl] (PTA = 1,3,5-triaza-7-phosphaadamantane), has revealed that the solvent takes an active part in lowering the energy barriers of the overallheterolytic splitting of the H-H bond. PTA itself promotes the heterolytic activation of the Ru(
2-H2)bond through one of its nitrogen atoms via a solvent-mediated intramolecular proton transfer.
2-H2)bond through one of its nitrogen atoms via a solvent-mediated intramolecular proton transfer.