Comparative DFT analysis of ligand and solvent effects on the mechanism of H<inf>2</inf> activation in water mediated by half-sandwich complexes [Cp′Ru(PTA)<inf>2</inf>Cl] (Cp′ = C<inf>5</inf>H<inf>5</inf>, C <inf>5</inf>Me<inf>5</inf>; PTA = 1,3,5-triaza-7-phosphaadamantane)

Gábor Kovács, Andrea Rossin, Luca Gonsalvi, Agustí Lledós, Maurizio Peruzzini

Research output: Contribution to journalArticleResearchpeer-review

25 Citations (Scopus)

Abstract

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. © 2010 American Chemical Society.
Original languageEnglish
Pages (from-to)5121-5131
JournalOrganometallics
Volume29
Issue number21
DOIs
Publication statusPublished - 8 Nov 2010

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