Department of Chemistry and Applied Biosciences, ETH Zürich, Laboratory of Inorganic Chemistry, Wolfgang Pauli Strasse 10, 8093, Zürich, Switzerland.
Department of Chemistry and Applied Biosciences, ETH Zürich, Laboratory of Physical Chemistry, Wolfgang Pauli Strasse 10, 8093, Zürich, Switzerland.
Angew Chem Int Ed Engl. 2016 Jan 26;55(5):1854-8. doi: 10.1002/anie.201509288. Epub 2015 Dec 22.
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.
在温和条件下，使用负载量低的铑配合物作为催化剂，以 N2O 作为氢受体实现了醇的氧化。两种不同的方法可分别形成相应的羧酸或酯。反应的唯一副产物为 N2 和水。通过密度泛函理论（DFT）计算支持的机理研究表明，N2O 的氧原子通过插入铑氨基氢化物物种的 Rh-H 键转移到金属中心，生成铑羟络合物作为关键中间体。
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