Premium
An In‐Depth Mechanistic Study of Ru‐Catalysed Aqueous Methanol Dehydrogenation and Prospects for Future Catalyst Design
Author(s) -
Govindarajan Nitish,
Sinha Vivek,
Trincado Monica,
Grützmacher Hansjörg,
Meijer Evert Jan,
Bruin Bas
Publication year - 2020
Publication title -
chemcatchem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.497
H-Index - 106
eISSN - 1867-3899
pISSN - 1867-3880
DOI - 10.1002/cctc.202000057
Subject(s) - dehydrogenation , chemistry , catalysis , aqueous solution , reactivity (psychology) , catalytic cycle , hydride , solvent , methanol , photochemistry , medicinal chemistry , combinatorial chemistry , hydrogen , organic chemistry , medicine , alternative medicine , pathology
Herein we provide mechanistic insights into the dehydrogenation of aqueous methanol catalysed by the [Ru(trop 2 dae)] complex (which is in‐situ generated from [Ru(trop 2 dad)], trop 2 dad=1,4‐bis(5H‐dibenzo[a,d]cyclohepten‐5‐yl)‐1,4‐diazabuta‐1,3‐diene), established by density functional theory based molecular dynamics (DFT‐MD) and static DFT calculations incorporating explicit solvent molecules. The aqueous solvent proved to participate actively in various stages of the catalytic cycle including the catalyst activation process, and the key reaction steps involving C−H activation and hydrogen production. The aqueous solvent forms an integral part of the reactive system for the C−H activation steps in the [Ru(trop 2 dae)] system, with strong hydrogen bond interactions with the anionic oxygen (RO − , R=CH 3 , CH 2 OH, HCO) and hydride moieties formed along the reaction pathway. In contrast to the [Ru(trop 2 dad)] catalyst, C−H activation and hydrogen production does not proceed via a metal‐ligand cooperative pathway for the [Ru(trop 2 dae)] system. The pK a of the coordinated amine donors in these complexes provides a rationale for the divergent reactivity, and the obtained mechanistic information provides new guidelines for the rational design of active and additive free catalytic systems for aqueous methanol dehydrogenation.