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

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• 作者：Gabriele Manca ; Irene Mellone ; Federica Bertini ; Maurizio Peruzzini ; Luca Rosi ; D枚rthe Mellmann ; Henrik Junge ; Matthias Beller ; Andrea Ienco ; Luca Gonsalvi
• 刊名：Organometallics
• 出版年：2013
• 出版时间：December 9, 2013
• 年：2013
• 卷：32
• 期：23
• 页码：7053-7064
• 全文大小：647K
• 年卷期：v.32,no.23(December 9, 2013)
• ISSN：1520-6041

文摘

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(魏⁴-NP₃)Cl₂] (1) and [Ru(魏³-triphos)(MeCN)₃](PF₆)₂ (2路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.