Inner- versus Outer-Sphere Ru-Catalyzed Formic Acid Dehydrogenation: A Computational Study
Organometallics2013Vol. 32(23), pp. 7053–7064
Citations Over TimeTop 13% of 2013 papers
Gabriele Manca, Irene Mellone, F. Bertini, Maurizio Peruzzini, Luca Rosi, Dörthe Mellmann, Henrik Junge, Matthias Beller, Andrea Ienco, Luca Gonsalvi
Abstract
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.
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