AI Article Synopsis
- Researchers investigated how different NHC ligands affect the performance of Ru(II)-NHC catalysts in hydride-transfer reactions, particularly in transfer hydrogenation.
- The study compared various precatalysts, showing that an electron-rich ligand led to improved performance in ketone reduction, while a bulky triazolylidene ligand excelled in aldehyde reduction.
- This is the first detailed analysis focusing on the stereoelectronic properties of NHC ligands in Ru(II)-catalyzed reactions across diverse unsaturated substrates.
Article Abstract
In an effort to develop efficient Ru(II)-NHC-based catalyst considering their stereoelectronic effect for hydride-transfer reaction, we found that the ancillary NHC ligand can play a significant role in its catalytic performance. This effect is demonstrated by comparing the activity of two different types of orthometalated precatalysts of general formula [( p-cymene)(NHC)Ru(X)] (NHC = an imidazolylidene-based ImNHC, compound 2a-c, or a mesoionic triazolylidene-based tzNHC, compound 4) in transfer hydrogenation of carbonyl substrates. The electron-rich precatalyst, 2c, containing p-OMe-substituted NHC ligand performed significantly better than both unsubstituted complex 2a and p-CF substituted electron-poor complex 2b in ketone reduction. Whereas bulky mesoionic triazolylidene ligand containing complex 4 was found to be superior catalyst for aldehyde reduction and the precatalyst 2a is more suitable for the selective transfer hydrogenation of a wide range of aromatic aldimines to amines. To the best of our knowledge, this is the first systematic study on the effect of stereoelectronic tuning of ancillary orthometalated NHC ligand in Ru(II)-catalyzed transfer hydrogenations of various types of unsaturated compounds with broad substrate scope.
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| http://dx.doi.org/10.1021/acs.inorgchem.8b02246 | DOI Listing |
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