Synthesis and catalytic alcohol oxidation and ketone transfer hydrogenation activity of donor-functionalized mesoionic triazolylidene ruthenium(II) complexes

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Title: Synthesis and catalytic alcohol oxidation and ketone transfer hydrogenation activity of donor-functionalized mesoionic triazolylidene ruthenium(II) complexes
Authors: Delgado-Rebollo, Manuela
Canseco-Gonzalez, Daniel
Hollering, Manuela
Müller-Bunz, Helge
Albrecht, Martin
Permanent link: http://hdl.handle.net/10197/6591
Date: 2014
Abstract: We report on the synthesis of a variety of C,E-bidentate triazolylidene ruthenium complexes that comprise different donor substituents E (E=C: phenyl anion; E=O: carboxylate, alkoxide; E=N: pyridine at heterocyclic carbon or nitrogen). Introduction of these donor functionalities is greatly facilitated by the synthetic versatility of triazoles, and their facile preparation routes. Five different complexes featuring a C,E-coordinated ruthenium center with chloride/cymene spectator ligands and three analogous solvento complexes with MeCN spectator ligands were prepared and evaluated as catalyst precursors for direct base- and oxidant-free alcohol dehydrogenation, and for transfer hydrogenation using basic iPrOH as a source of dihydrogen. In both catalytic reactions, the neutral/mono-cationic complexes with chloride/cymene spectator ligands performed better than the solvento ruthenium complexes. The donor functionality had a further profound impact on catalytic activity. For alcohol dehydrogenation, the C,C-bidentate phenyl-triazolylidene ligand induced highest conversions, while carboxylate or pyridine donor sites gave only moderate activity or none at all. In contrast, transfer hydrogenation is most efficient when a pyridyl donor group is linked to the triazolylidene via the heterocyclic carbon atom, providing turnover frequencies as high as 1400 h-1 for cyclohexanone transfer hydrogenation. The role of the donor group is discussed in mechanistic terms.
Funding Details: European Research Council
Science Foundation Ireland
Type of material: Journal Article
Publisher: Royal Society of Chemistry
Copyright (published version): 2014 The Royal Society of Chemistry
Keywords: Ruthenium cymene complexesSolvento complexesKetone transfer hydrogenationDirect alcohol oxidation
DOI: 10.1039/c3dt53052c
Language: en
Status of Item: Peer reviewed
Appears in Collections:Chemistry Research Collection

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