title: Nitrous Oxide as a Hydrogen Acceptor for the Dehydrogenative Coupling of Alcohols.
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.
authors.affiliation: Department of Chemistry and Applied Biosciences, ETH Zürich, Laboratory of Inorganic Chemistry, Wolfgang Pauli Strasse 10, 8093, Zürich, Switzerland. gianetti@inorg.chem.ehtz.ch.
authors.forename: Thomas L
authors.initials: TL
authors.lastname: Gianetti
authors.affiliation: Department of Chemistry and Applied Biosciences, ETH Zürich, Laboratory of Inorganic Chemistry, Wolfgang Pauli Strasse 10, 8093, Zürich, Switzerland.
authors.forename: Samuel P
authors.initials: SP
authors.lastname: Annen
authors.affiliation: Department of Chemistry and Applied Biosciences, ETH Zürich, Laboratory of Inorganic Chemistry, Wolfgang Pauli Strasse 10, 8093, Zürich, Switzerland.
authors.forename: Gustavo
authors.initials: G
authors.lastname: Santiso-Quinones
authors.affiliation: Department of Chemistry and Applied Biosciences, ETH Zürich, Laboratory of Physical Chemistry, Wolfgang Pauli Strasse 10, 8093, Zürich, Switzerland. markus.reiher@phys.chem.ethz.ch.
authors.forename: Markus
authors.initials: M
authors.lastname: Reiher
authors.affiliation: Institute of Chemistry: Metalorganics and Inorganic Materials, Technical University Berlin, Strasse des 17. Juni 135, 10623, Berlin, Germany.
authors.forename: Matthias
authors.initials: M
authors.lastname: Driess
authors.affiliation: Department of Chemistry and Applied Biosciences, ETH Zürich, Laboratory of Inorganic Chemistry, Wolfgang Pauli Strasse 10, 8093, Zürich, Switzerland. gruetzmacher@inorg.chem.ethz.ch.
authors.forename: Hansjörg
authors.identifier: http://orcid.org/0000-0002-1531-8906
authors.initials: H
authors.lastname: Grützmacher
keywords: alcohols; catalysis; coupling reactions; dehydrogenation; nitrous oxide; rhodium