Role of the chemically non-innocent ligand in the catalytic formation of hydrogen and carbon dioxide from methanol and water with the metal as the spectator

Journal of the American Chemical Society
Haixia Li, Michael B Hall

Abstract

The catalytic mechanism for the production of H2 and CO2 from CH3OH and H2O by [K(dme)2][Ru(H) (trop2dad)] (K(dme)2.1_exp) was investigated by density functional theory (DFT) calculations. Since the reaction occurs under mild conditions and at reasonable rates, it could be considered an ideal way to use methanol to store hydrogen. The predicted mechanism begins with the dehydrogenation of methanol to formaldehyde through a new ligand-ligand bifunctional mechanism, where two hydrogen atoms of CH3OH eliminate to the ligand's N and C atoms, a mechanism that is more favorable than the previously known mechanisms, β-H elimination, or the metal-ligand bifunctional. The key initiator of this first step is formed by migration of the hydride in 1 from the ruthenium to the meta-carbon atom, which generates 1″ with a frustrated Lewis pair in the ring between N and C. Hydroxide, formed when 1″ cleaves H2O, reacts rapidly with CH2O to give H2C(OH)O(-), which subsequently donates a hydride to 6 to generate HCOOH and 5. HCOOH then protonates 5 to give formate and a neutral complex, 4, with a fully hydrogenated ligand. The hydride of formate transfers to 6, releasing CO2. The fully hydrogenated complex, 4, is first deprotonated by OH(-) to for...Continue Reading

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Citations

Aug 24, 2016·Journal of the American Chemical Society·Wusheng GuoArjan W Kleij
Oct 21, 2016·Journal of the American Chemical Society·Elisabetta AlbericoMatthias Beller
Jul 12, 2017·Dalton Transactions : an International Journal of Inorganic Chemistry·Kyounghoon LeeScott R Daly
Apr 14, 2016·Chemical Communications : Chem Comm·Demyan E ProkopchukHansjörg Grützmacher
Aug 2, 2018·Organic & Biomolecular Chemistry·Yuan-Ye JiangSiwei Bi
May 29, 2019·Organic & Biomolecular Chemistry·Yuan-Ye JiangSiwei Bi
Apr 30, 2017·Nature Communications·M TrincadoHansjörg Grützmacher
Apr 4, 2021·Chemistry : a European Journal·Philip JunkerRainer Streubel
Dec 7, 2019·The Journal of Organic Chemistry·Yulei ZhaoYuanye Jiang

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