期刊
INORGANIC CHEMISTRY
卷 50, 期 21, 页码 10572-10580出版社
AMER CHEMICAL SOC
DOI: 10.1021/ic200205e
关键词
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资金
- National Natural Science Foundation of China [21073086, 20833003]
- National Basic Research Program [2011CB808501]
Density functional theory calculations were performed to elucidate the mechanism of dehydrogenative coupling of primary alcohols and amines mediated by a PNN-Ru(II) hydride complex (PNN = (2-(di-tert-butylphosphinomethyl)-6-(diethylaminomethyl)pyridine)). A plausible reaction pathway was proposed which contains three stages: (1) The alcohol dehydrogenation reaction to generate the aldehyde and H-2; (2) The aldehyde-amine condensation reaction to form the hemiaminal intermediate; (3) The dehydrogenation process of the hemiaminal intermediate to yield the final amide product with the liberation of H-2. The first and third stages occur via a similar pathway: (a) Proton transfer from the substrate to the PNN ligand; (b) Intramolecular rearrangement of the deprotonated substrate to form an anagostic complex; (c) Hydride transfer from the deprotonated substrate to the Ru center to yield the trans-dihydride intermediate and the aldehyde (or amide); (d) Benzylic proton migration from the PNN ligand to the metal center forming a dihydrogen complex and subsequent H-2 liberation to regenerate the catalyst. In all these steps, the metal-ligand cooperation plays an essential role. In proton transfer steps (a) and (d), the metal-ligand cooperation is achieved through the aromatization/dearomatization processes of the PNN ligand. 'While in steps (b) and (c), their collaboration are demonstrated by the formation of an anagostic interaction between Ru and the C-H bond and two ionic hydrogen bonds supported by the PNN ligand.
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