Water-Assisted H−H Bond Splitting Mediated by [CpRu(PTA)₂Cl] (PTA=1,3,5-triaza-7-phosphaadamantane). A DFT Analysis

Abstract

A DFT study using a “discrete-continuum” modeling of the reaction medium, employed to unravel the role of water in the activation of dihydrogen by [CpRu(PTA) 2 Cl] (PTA = 1,3,5-triaza-7-phosphaadamantane), has revealed that the solvent takes an active part in lowering the energy barriers of the overall heterolytic splitting of the H−H bond. PTA itself promotes the heterolytic activation of the Ru(η 2 -H 2 ) bond through one of its nitrogen atoms via a solvent-mediated intramolecular proton transfer.