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Nitrous Oxide as a Hydrogen Acceptor for the Dehydrogenative Coupling of Alcohols |
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| Authors: | Dr Thomas L Gianetti Dr Samuel P Annen Dr Gustavo Santiso‐Quinones Prof?Dr Markus Reiher Prof?Dr Matthias Driess Prof?Dr Hansjörg Grützmacher |
| Institution: | 1. Department of Chemistry and Applied Biosciences, ETH Zürich, Laboratory of Inorganic Chemistry, Zürich, Switzerland;2. Department of Chemistry and Applied Biosciences, ETH Zürich, Laboratory of Physical Chemistry, Zürich, Switzerland;3. Institute of Chemistry: Metalorganics and Inorganic Materials, Technical University Berlin, Berlin, Germany |
| Abstract: | The oxidation of alcohols with N2O as the hydrogen acceptor was achieved with low catalyst loadings of a rhodium complex that features a cooperative bis(olefin)amido ligand under mild conditions. Two different methods enable the formation of either the corresponding carboxylic acid or the ester. N2 and water are the only by‐products. Mechanistic studies supported by DFT calculations suggest that the oxygen atom of N2O is transferred to the metal center by insertion into the Rh?H bond of a rhodium amino hydride species, generating a rhodium hydroxy complex as a key intermediate. |
| Keywords: | alcohols catalysis coupling reactions dehydrogenation nitrous oxide rhodium |