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Inner- versus Outer-Sphere Ru-Catalyzed Formic Acid Dehydrogenation: A Computational Study

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journal contribution
posted on 09.12.2013, 00:00 by Gabriele Manca, Irene Mellone, Federica Bertini, Maurizio Peruzzini, Luca Rosi, Dörthe Mellmann, Henrik Junge, Matthias Beller, Andrea Ienco, Luca Gonsalvi
A detailed hybrid density functional theory study was carried out to clarify the mechanism of Ru-catalyzed dehydrogenation of formic acid in the presence of the octahedral complexes [Ru­(κ4-NP3)­Cl2] (1) and [Ru­(κ3-triphos)­(MeCN)3]­(PF6)2 (2·PF6) [NP3 = N­(CH2CH2­PPh2)3, triphos = MeC­(CH2­PPh2)3]. It was shown that Ru-hydrido vs Ru-formato species are pivotal to bringing about the efficient release of H2 and CO2 following either a metal-centered (inner-sphere) or a ligand-centered (outer-sphere) pathway, respectively.