Water-assisted H-H bond splitting mediated by [CpRu(PTA)2Cl] (PTA=1,3,5-triaza-7-phosphaadamantane). A DFT analysis.

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)2Cl] (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(eta2-H2) bond through one of its nitrogen atoms via a solvent-mediated intramolecular proton transfer