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Highly Efficient and Selective Hydrogenation of Aldehydes: A Well-Defined Fe(II) Catalyst Exhibits Noble-Metal Activity

The synthesis and application of [Fe­(PNPMe-iPr)­(CO)­(H)­(Br)] and [Fe­(PNPMe-iPr)­(H)2(CO)] as catalysts for the homogeneous hydrogenation of aldehydes is described. These systems were found to be among the most efficient catalysts for this process reported to date and constitute rare examples of...

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Bibliographic Details
Published in:ACS catalysis 2016-04, Vol.6 (4), p.2664-2672
Main Authors: Gorgas, Nikolaus, Stöger, Berthold, Veiros, Luis F, Kirchner, Karl
Format: Article
Language:English
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Summary:The synthesis and application of [Fe­(PNPMe-iPr)­(CO)­(H)­(Br)] and [Fe­(PNPMe-iPr)­(H)2(CO)] as catalysts for the homogeneous hydrogenation of aldehydes is described. These systems were found to be among the most efficient catalysts for this process reported to date and constitute rare examples of a catalytic process which allows selective reduction of aldehydes in the presence of ketones and other reducible functionalities. In some cases, TONs and TOFs of up to 80000 and 20000 h–1, respectively, were reached. On the basis of stoichiometric experiments and computational studies, a mechanism which proceeds via a trans-dihydride intermediate is proposed. The structure of the hydride complexes was also confirmed by X-ray crystallography.
ISSN:2155-5435
2155-5435
DOI:10.1021/acscatal.6b00436