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Nitrous Oxide as a Hydrogen Acceptor for the Dehydrogenative Coupling of Alcohols
Thomas L Gianetti1, Samuel P Annen2, Gustavo Santiso-Quinones2
1Department of Chemistry and Applied Biosciences, ETH Zürich, Laboratory of Inorganic Chemistry, Wolfgang Pauli Strasse 10, 8093, Zürich, Switzerland. gianetti@inorg.chem.ehtz.ch.
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.
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